DE3016340A1 - METHOD FOR gluing cation exchange membranes made of fluorinated polymers - Google Patents
METHOD FOR gluing cation exchange membranes made of fluorinated polymersInfo
- Publication number
- DE3016340A1 DE3016340A1 DE19803016340 DE3016340A DE3016340A1 DE 3016340 A1 DE3016340 A1 DE 3016340A1 DE 19803016340 DE19803016340 DE 19803016340 DE 3016340 A DE3016340 A DE 3016340A DE 3016340 A1 DE3016340 A1 DE 3016340A1
- Authority
- DE
- Germany
- Prior art keywords
- cation exchange
- exchange membranes
- fluorinated polymers
- membranes made
- gluing
- 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.)
- Withdrawn
Links
- 239000012528 membrane Substances 0.000 title claims description 31
- 238000005341 cation exchange Methods 0.000 title claims description 17
- 229920002313 fluoropolymer Polymers 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 7
- 238000004026 adhesive bonding Methods 0.000 title claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
-
- 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
- C08J5/2287—After-treatment
- C08J5/2293—After-treatment of fluorine-containing membranes
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (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
Das Verkleben von Kationenaustauschermembranen ist technisch von großer Bedeutung. Kationenaustauschermembranen müssen in beliebigen Formen und ausreichend großen Abmessungen hergestellt werden. Ferner müssen bei der Handhabung beschädigte Kationenaustauschermembranen repariert bzw. ausgebessert werden.The bonding of cation exchange membranes is of great technical importance. Cation exchange membranes must be made in any shape and large enough. Also need in handling damaged cation exchange membranes are repaired or repaired.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zum Verkleben von Kationenaustauschermembranen aus fluorierten Polymerisaten zu entwickeln, das es gestattet, Kationenaustauschermembranen in jeder gewünschten Form und in ausreichenden Größen herzustellen sowie beschädigte Kationenaustauschermembranen zu reparieren. Diese Aufgabe wird gemäß dem Kennzeichen des Patentanspruchs gelöst.The invention is based on the object of a method for gluing together cation exchange membranes made of fluorinated To develop polymers that allow cation exchange membranes in any desired shape and in sufficient sizes as well as damaged cation exchange membranes to repair. This object is achieved according to the characterizing part of the patent claim.
Die Lösung der Aufgabe beruht auf dem überraschenden Befund, daß Membranen aus fluorierten Polymerisaten mit -COOH Gruppen an der Matrix, die mindestens an ihrer einen Seite mit einem tertiären Amin oder einer quartären Ammoniumbase behandelt worden sind, sich unter Wärmeanwendung verpressen lassen. Auf diese Weise werden die Membranen dauerhaft miteinander verbunden bzw. verklebt.The solution to the problem is based on the surprising finding that membranes made from fluorinated polymers with -COOH groups on the matrix, which is treated on at least one side with a tertiary amine or a quaternary ammonium base can be pressed with the application of heat. In this way, the membranes become permanent with each other connected or glued.
Kationenaustauschermembranen mit Carboxylgruppen an der Matrix sind bekannt. Die Matrix kann aus einem Perfluorkohlenstoff bestehen. Die Carboxylgruppen können an beiden Seiten der Membran oder nur an einer Seite bzw. Oberfläche der Membran angeordnet sein. Die Dicke der Carboxylgruppen enthaltenden Schicht beträgt mindestens 1 Mikron, vorzugsweise mindestens 10 Mikron. Die Carboxylgruppen an der Matrix müssen freie Carboxylgruppen sein. Kationenaustauschermembranen mit Carboxylgruppen in der AlkalimetallformCation exchange membranes with carboxyl groups on the matrix are known. The matrix can be made from a perfluorocarbon exist. The carboxyl groups can be on both sides of the membrane or only on one side or surface be arranged on the membrane. The thickness of the carboxyl group-containing layer is at least 1 micron, preferably at least 10 microns. The carboxyl groups on the matrix must be free carboxyl groups. Cation exchange membranes with carboxyl groups in the alkali metal form
L 030046/0767 J L 030046/0767 J.
"3- 30Ί6340Π " 3 - 30,6340 Π
können nicht in der. Wärme verarbeitet werden.can not in the. Heat can be processed.
Die Kationenaustauschermembranen auf der Basis von fluorierten Polymerisaten mit freien Carboxylgruppen werden mit einem tertiären Amin oder einer quartären Ammoniumbase behandelt. Ka.tionenaustauscherrnembranen aus fluorierten Polymerisaten mit Carboxylgruppen in der Alkalimetallsalzform lassen sich selbst nach Behandlung mit einem tertiären Amin oder einer quartären Ammoniumbase nicht in der Wärme verarbeiten bzw.. verpressen.The cation exchange membranes based on fluorinated polymers with free carboxyl groups are with treated with a tertiary amine or a quaternary ammonium base. Ion exchange membranes made from fluorinated polymers with carboxyl groups in the alkali metal salt form can be obtained even after treatment with a tertiary amine or a quaternary ammonium base do not process or .. press in the heat.
In der JA-OS 49 394/1975 ist ein Verfahren zum Verkleben von Kationenaustauschermembranen aus fluorierten Polymerisaten mit Sulfonsäure- oder Sulfonamidgruppen bekannt.In JA-OS 49 394/1975 there is a method for gluing cation exchange membranes made from fluorinated polymers known with sulfonic acid or sulfonamide groups.
Bei diesem Verfahren werden die Membranen mit einem tertiären Amin, einer quartären Ammoniumbase oder deren Salzen behandelt und sodann unter Anwendung von Wärme miteinander verschlossen. Kationenaustauschermembranen aus fluorierten Polymerisaten mit Carboxylgruppen an der Matrix verhal-In this process, the membranes are coated with a tertiary amine, a quaternary ammonium base or their salts treated and then sealed together with the application of heat. Cation exchange membranes made from fluorinated Polymers with carboxyl groups on the matrix
ten sich etwas anders als die Kationenaustauschermembranen mit Sulfonsäure- oder Sulfonamidgruppen. Die Membranen mit Carboxylgruppen in der Alkalimetallsalzform lassen sich, wie bereits ausgeführt, auch nach Behandlung mit einem Salz eines tertiären Amins oder einer quartären Ammoniumbaseten different from the cation exchange membranes with sulfonic acid or sulfonamide groups. The membranes with Carboxyl groups in the alkali metal salt form can, as already stated, also after treatment with a salt a tertiary amine or a quaternary ammonium base
nicht unter Wärmeanwendung miteinander verpressen und verkleben. do not press and stick together with the application of heat.
Es ist nicht bekannt, warum Kationenaustauschermembranen des Carbonsäuretyps, die mit einem tertiären Amin oder einerIt is not known why cation exchange membranes of the carboxylic acid type formed with a tertiary amine or a
quartären Ammoniumbase behandelt worden sind, sich unterquaternary ammonium base have been treated under
Wärmeanwendung miteinander verpressen und dauerhaft verkleben lassen, während Kationenaustauschermembranen des Carbonsäuretyps in der Alkalimetallsalzform selbst nach Behandlung mit einem Salz eines tertiären Amins oder einer 35The application of heat can be pressed together and permanently bonded, while the cation exchange membranes of the Carboxylic acid type in the alkali metal salt form even after treatment with a salt of a tertiary amine or a 35
quartären Ammoniumbase sich nicht auf diese Weise verkleben lassen. Vermutlich erfolgt im ersten Fall eine Neutra-Quaternary ammonium base cannot be glued in this way. Presumably in the first case a neutral
030046/0767 J 030046/0767 J.
lisationsreaktion an den. freien Carboxylgruppen, während im letztgenannten Fall eine doppelte Umsetzung erfolgen muß, die nicht vollständig abläuft.lization reaction to the. free carboxyl groups, while im In the latter case, a double conversion must take place, which does not run completely.
Das verpressen unter Wärmeanwendung wird- beispielsweise in einer beheizten Presse bei Temperaturen von 200 bis 300°C, vorzugsweise 230 bis 26O°C durchgeführt. Der Druck liegt im Bereich von 2 bis T50 kg/cm2 r vorzugsweise TO bis 100 kg/cm* Die PreSzeit kann T bis 30" Minutenr vorzugsweise 3 bis 10 fTinuten betragen-The pressing with the application of heat is carried out, for example, in a heated press at temperatures of 200 to 300 ° C., preferably 230 to 260 ° C. The pressure is in the range of 2 to T50 kg / cm 2 r TO preferably up to 100 kg / cm * The T can PreSzeit to 30 "minutes is preferably 3 to 10 r fTinuten betragen-
Die Beispiele erläutern die Erfindung..The examples illustrate the invention.
Kafeionenaustauschermembranen des Carbonsäuretypsp die durch beitisei.1ti.ges Denaturieren der entsprechenden Kationenaus— feaaischesanembranen des Suifonsäuretyps erhalten worden sind K weardem mit: Salzsäure in die Membranen mit: freiem Carboxylgruppen!. uEierfuhrt:.. EEiese Membranen werden sodann SO) MinutenKafeionenaustauschermembranen of Carbonsäuretypsp the feaaischesanembranen beitisei.1ti.ges by denaturing the corresponding cation-Suifonsäuretyps the obtained K weardem with: hydrochloric acid in the membranes: free carboxyl groups !. uEierfuhrt: .. These membranes are then SO) minutes
20) mit einer 5Qpro;zentigen wäßrigen Lösung von Methanol behan— delit,, dlie· Q)r2 Mfctl ITetra-n-butylammaniumhydiroxxd enthält» Soxäaimi werdleni düe Membranen aufeinandergelegt und. 5 Minu-teiL bsi. 25Q)^C TiTTTf?? einem Druck: von SO1 kgr/cm? roi.teinandear ver— gareffit« D)ie erhaOIfceEcen verfelebvfcenL Mfembranem werdlem 1! Mönaifc fx® eine Salzlösung? getrauehifcp wdle sie Im einer· eEElaraJUcaüLiL— elefefcarcilyseZieHe ansfäöllfc., Es fcanni keilt fibslasen der; \rerfelebvEEni— gem bBhtfc20) having a 5Qpro; zentigen aqueous solution of methanol behan- delit ,, dlie · Q) r 2-n-Mfctl ITetra butylammaniumhydiroxxd contains "Soxäaimi werdleni DCE membranes stacked and. 5 minute part to 25Q) ^ C TiTTTf ?? a pressure: from SO 1 kgr / cm? roi.teinandear ver— gareffit «T) he obtainCEEcen desfelebvfcenL Mfembranem will be 1! Mönaifc fx® a saline solution? she wdle in a · eEElaraJUcaüLiL— elefefcarcilyseZieHe ansfäöllfc., It fcanni wedges fibslasen der; \ rerfelebvEEni— according to bBhtfc
Beispiel 2
30) T^afciianigimaimsdr^TiEscrfTfiiTmpjimThr^ des GTarbQHisä\uretypSp düe
EteiaiatuarieruitgT vom Emtiane^auistaiUiScfceiriai des SuJL—
erirailTrerii worxiemi sindip werden nrjLt; Salzsäuare fee—
. Äuuf düese Weise werdem Membrranem nrjit; freiem Caarbcs—
erhalten. Piese Membranem werdem 303 MoLnurteni nnit;
einer SOpiDjszeimfcigiem wäUBirigieni EäcsaiEngf warn Mfetirano)!Example 2
30) T ^ afciiani gimaim sdr ^ TiEscrfTfiiTmpjimThr ^ des GTarbQHisä \ uretypSp düe EteiaiatuarieruitgT vom Emtiane ^ auistaiUiScfceiriai des SuJL— erirailTrerii worxiemi sindi p be nrjLt; Hydrochloric acid fee—. In this way Membrranem nrjit; free Caarbcs— received. These membranes become 303 MoLnurteni nnit; a SOpiDjszeimfcigiem wäUBirigieni EäcsaiEngf warn Mfetirano)!
düe 0)^2 Mb)I Tfetea-^m-MRt^lsmxmsi^xmsk^äirEi^ln. enitEiäJLit. Soxiamnidüe 0) ^ 2 Mb) I Tfetea- ^ m-MRt ^ lsmxmsi ^ xmsk ^ äirEi ^ ln. enitEiäJLit. Soxiamni
L-. d~. ^fc. 0^. JMv gr jf%\ K Λ 9Ί} 4& ^w] L-. d ~. ^ fc. 0 ^. JMv gr jf% \ K Λ 9Ί} 4 & ^ w]
1 werden diese Seiten der behandelten Membranen aufeinandergelegt und bei 24O°C unter einem Druck von 70 kg/cm2 miteinander verpreßt. Die verklebten Membranen werden gemäß Beispiel 1 in eine Salzlösung getaucht. Auch nach 1 Monat1, these sides of the treated membranes are placed on top of one another and pressed together at 240 ° C. under a pressure of 70 kg / cm 2 . The bonded membranes are immersed in a salt solution according to Example 1. Even after 1 month
5 kann kein Ablösen der Verklebungen beobachtet werden.5 no detachment of the bonds can be observed.
L 030046/0767 J L 030046/0767 J.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5315579A JPS55145539A (en) | 1979-04-28 | 1979-04-28 | Joining method of cation exchange membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3016340A1 true DE3016340A1 (en) | 1980-11-13 |
Family
ID=12934946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19803016340 Withdrawn DE3016340A1 (en) | 1979-04-28 | 1980-04-28 | METHOD FOR gluing cation exchange membranes made of fluorinated polymers |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS55145539A (en) |
| DE (1) | DE3016340A1 (en) |
| FR (1) | FR2455063A1 (en) |
| GB (1) | GB2052381A (en) |
| IT (1) | IT1144083B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2121352B (en) * | 1982-05-25 | 1986-03-19 | Chlorine Eng Corp Ltd | Bonding of cation exchange membrane |
| FR2617760B1 (en) * | 1987-07-10 | 1989-11-24 | Souriau & Cie | PROCESS FOR ASSEMBLING PARTS OF POLYMERIC MATERIALS |
| US5855977A (en) * | 1996-08-26 | 1999-01-05 | Minnesota Mining And Manufacturing Company | Multi-layer compositions comprising a fluoropolymer |
-
1979
- 1979-04-28 JP JP5315579A patent/JPS55145539A/en active Pending
-
1980
- 1980-02-13 GB GB8004894A patent/GB2052381A/en not_active Withdrawn
- 1980-04-21 FR FR8008895A patent/FR2455063A1/en not_active Withdrawn
- 1980-04-24 IT IT48507/80A patent/IT1144083B/en active
- 1980-04-28 DE DE19803016340 patent/DE3016340A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| IT1144083B (en) | 1986-10-29 |
| IT8048507A0 (en) | 1980-04-24 |
| JPS55145539A (en) | 1980-11-13 |
| GB2052381A (en) | 1981-01-28 |
| FR2455063A1 (en) | 1980-11-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |