• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A fluorinated polymer having pendant cation exchange groups selected from sulfonic acid, carboxylic acid or sulfonamide groups, or their salts is modified with a sulfonium compound and, or a phosphonium compound for substitution of the counter-ions of the cation exchange groups with sulfonium ions and or phosphonium ions. The polymers treated in this manner are improved in melt-flow characteristic to make fusion bonding between these polymers possible. The process is particularly suitable for repairing damaged cation exchange membranes for use in chlor-alkali electrolytic cells to advantageously elongate the life of the membranes.
    公开号:SU1069629A3
    申请号:SU813284352
    申请日:1981-05-08
    公开日:1984-01-23
    发明作者:Тсусима Сакаи；Сагами Хироси
    申请人:Асахи Касеи Когио Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for fusion of fluorocarbon-type cation-exchange membranes. Fluorocarbon-type cation-exchange membranes having functional groups such as sulfonic acid groups, carboxylic acid groups, sulfamide groups, etc., are used as diaphragms in electrolysis in the preparation of alkali. During operation, these ion-exchange membranes may have damages, such as rupture, puncture, cracking, or others, due to which they must be repaired for reuse, thus increasing the service life of the expensive fluorocarbon type ion-exchange membrane. A known method of repairing a membrane in which an overlay of the same membrane as the membrane to be repaired is applied to the damaged part of the membrane for fusion bonding, and the fusion bonding is carried out by heating the membranes in the presence of an aqueous medium. Cll This method can be successfully used to fuse the damaged small sizes, but it is not satisfactory for fusion of the damaged areas of relatively large dimensions, since this process must be carried out s When the temperature and pressure. Closest to the invention is a method of combining fluorinated membranes of a perfluorinated polymer containing side groups of the general formula) 0-VCl jbaX CF, where 1 is O or 1 -, m is 0-5, X is a sulfonic acid group, amide sulfide, carboxylic acid or their salt, by fusing at elevated temperature and pressure of C21. To fuse, it is necessary to change the temperature to above ZOOC, which is undesirable, since the polymer can be destroyed in this case. The aim of the invention is to simplify the connection technology. The goal is achieved in that according to the method of combining cation-exchange fluorocarbon membranes made of a perfluorinated polymer containing pendant groups of the general formula where 1 is 0 or 1 j, m is 0-5; X is a group of sulfonic acid, sulfamide, carboxylic acid or their salt, by fusing at elevated temperature and pressure, before fusing, the perfluorinated polymer is subjected to interaction with sulfonium or phosphonium ions. Preferably, the polymer is subjected to interaction of one of the joined membranes. As a sulfonium ion or a phosphonium ion, trimethylsulfonium ion or triethylsulfonium ion and tetramethyl or tetraethylphosphonium ion are used. Preferably, a membrane reinforced with polytetrafluoroethylene fibers is used as the membrane, and the core is fused at 240–270 ° C and a pressure of 7–10 kgf / cm, preferably under the influence of ultrasound with an amplitude of 120–200 µm 35 kgf / cm for 1-10 s. Using the proposed method, it is possible to easily manufacture a fluorocarbon-type cation-exchange membrane by combining into a product in the form of a cylinder or a bag. Such a product, respectively, can be installed, for example, on a finger-type electrolytic cell. The polymers from which the membranes are made are widely known and can be obtained both by copolymerizing the corresponding monomers and by chemical modification of the starting fluorinated copolymers. The invention can be effectively applied to the compound by fusing polymers of any desired shape, including membranes, granules, powders, etc. It is also effective for films reinforced with fibrous materials. Using sulfonium or phosphonium ions as counter-ions, it is possible to improve the melting flow rate of these polymers to such a limit that their compound can be easily made by fusion. Said sulfonium ion is represented by the formula (K55), where qd is an alkyl-methyl or aryl group. Typical examples are the trimethylsulfonium ion, the triethylsulfonium ion. The phosphonium ion is represented by the formula (Hi, P), where R is the same group. Replacement of counterions of cation-exchange groups in fluorinated polymers with sulfonium ions or phosphonium ions can be easily carried out provided that these fluorinated polymers come in contact with an aqueous solution of a sulfonium base or its salt, phosphonium base or its salt. Water is preferred as the solvent. To improve the solubility, a mixture of water and an organic solvent, such as an alcohol or ketone, can be used. When carrying out the replacement of counterions of cation-exchange groups in accordance with the ion-exchange method, the content of competing counter-ions (for example, Na, or other ions) should preferably be reduced to the lowest possible concentrations.
    The concentration of sulfonium and / or phosphonium ions in said solution can usually be in the range from 0.01 to 0.5 n.
    The result of the substitution depends on the degree of substitution. However, melting flow can be successfully improved by replacing counterions with at least 10% of all cation exchange groups, whereby the fusion compound can be made easier. Even with less than 10% substitution, you can get a positive result, but preferably at least 10% substitution. . In accordance with the invention, fluorinated polymers having cation exchange groups that need to be bonded to each other by bonding can be either coBepmeHHd identical to each other, or differ in different parameters, such as cation-exchange groups, equivalent or molecular weights, etc. . The effect of the invention is manifested even if the counterions of the cation-exchange groups in only one of the polymers that need to be fused are replaced by sulfonium and / or phosphonium ions. When the compound is made by fusing, counterions of cation-exchange groups are converted into at least one of these polymers, which need to be joined by fusion, into sulfonium ions and / or phosphonium ions before these polymers are compressed with heating or in wet or dry conditions.
    The proposed method, in particular, is very effective when used in such a process in which a small piece of polymer (hereinafter referred to as a GREEN patch) is placed on the damaged area for fusion bonding, since thus the sulfonium or phosphonium compound must only be treated with a pad.
    For heating, you can use a heating plate, ultrasonic, pulse heating, friction heating, high-frequency heating, and others. In terms of performance, the best of these is ultrasonic heating. The heating temperature and compression pressure, which depend on the molecular weight of these polymers, the presence of reinforcing materials, ion exchange groups used, configurations of polymers, the percentage substitution of sulfonium ions and / or phosphonium ions, cannot be determined unambiguously. However, generally speaking, fusion bonding can be carried out at 150-300 ° C, usually 240-260 ° C. Fusion bonding can be effectively carried out under
    pressure, usually 3-20 kg / cm, preferably 5-10 kg / cm. When using ultrasound, the recommended conditions are usually as follows:
    120–200 µm for the amplitude of oscillations 28–35 kg / cm for pressure and 1–10 s for the duration of exposure.
    Thus, fusion-bonded polymers are connected sufficiently firmly to be resistant to boiling with water, 5 n. an aqueous solution of sodium hydroxide or a mixture of water and methanol.
    Example 1. A 4 mm thick film made of a copolymer of tetrafluoroethylene and
     The CFi-CFDCFaCF C..f, 11th copolymerization ratio: 1500, in equivalent weight units, reinforced with polytetrafluoroethylene fibers, is treated with a solution containing 15% potassium hydroxide, 30% methanol and 55% water, to transform the side groups in the polymer in the group SOjK.
    Two strips of this polymer film are treated by immersion in 0.1 n. aqueous solution of trimethylsulfonium iodide at room temperature for 10 hours. In the wet state. These two strips overlap each other and are compressed with heating at a pressure of 10 kg / cm for 5 min. The resulting compound is resistant to adhesion to 5N. aqueous solution of caustic soda within 10 hours
    Example 2. A 0.3 mm thick film made from a copolymer of tetrafluoroethylene and CP2-1 POCP2CP () 0 (CP2)} 30 having a copolymerization ratio of 1100 in units of equivalent weight was subjected to saponification treatment under the same conditions as in Example 1, dl transformations of the COj F side groups in the polymer in the SOjK group. Two strips of this film are treated with 2 n. hydrochloric acid conversion
    权利要求:
    Claims (7)
    [1]
    CL.156-305, published. 1978 (prototype). (54) (57) /. METHOD FOR COMBINING CATION EXCHANGE FLUOROURBEOUS MEMBRANES made of perfluorinated polymer containing side groups of the general formula +0 (1 =, 0 = ^ 0 + (¾ ^,
    01 = J "
    Where 1 is 0 or 1 'for m is 0-5.
    x is a group of sulfonic acid, sulfamide, carboxylic acid or their salts, by fusion at elevated temperatures and pressure, characterized in that, in order to simplify the technology of the compound, the perfluorinated polymer is reacted with sulfonium or phosphonium ions before fusion.
    [2]
    2. The method according to claim 1, characterized in that the polymer is subjected to the interaction of one of the joined membranes.
    [3]
    3. The method according to claim 1, t and h and · · · and with the fact that as a sulfonium ion, trimethylsulfonium ion is used.
    [4]
    4. The method of Pop. 1, with the exception that tetramethyl or tetraethylphosphonium ion is used as the phosphonium ion.
    _ <i
    [5]
    5. The method according to claim 1, with the fact that as a membrane using a membrane reinforced with fibers of polytetrafluoroethylene.
    [6]
    6. The method pop.1 distinguish and with I d in that the alloying is carried membranes hours at 240-270 ° C and a pressure of 7-10 kgf / cm.
    [7]
    7. The method of pop. 1, characterized in that the fusion is carried out under the influence of ultrasound with an oscillation amplitude of 120-200 μm, a pressure of 28-35 kgf / cm for 1-10 s.
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    同族专利:
    公开号 | 公开日
    JPS56157432A|1981-12-04|
    CA1145236A|1983-04-26|
    EP0039897A1|1981-11-18|
    JPS6329695B2|1988-06-15|
    EP0039897B1|1984-08-22|
    US4339549A|1982-07-13|
    DE3165645D1|1984-09-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3146213A|1959-03-23|1964-08-25|Dow Chemical Co|Composition for use in solvent extraction process for the recovery of uranium and rare earth metals from aqueous solutions|
    DE2655145C2|1976-12-06|1985-10-03|Basf Ag, 6700 Ludwigshafen|Process for welding membranes made from fluorinated polymers|
    US4218275A|1978-02-03|1980-08-19|Olin Corporation|Method of sealing separators for electrolytic cells for alkali metal chloride brines|
    JPS6041085B2|1978-05-30|1985-09-13|Asahi Chemical Ind|
    US4284460A|1979-04-30|1981-08-18|Olin Corporation|Heat sealing untreated sulfonamide-type cation exchange membranes|
    US4290833A|1979-09-28|1981-09-22|Olin Corporation|Method for sealing cation exchange membranes of carboxylic acid type fluorinated polymers|JPS6411663B2|1980-11-29|1989-02-27|Asahi Chemical Ind|
    GB2121352B|1982-05-25|1986-03-19|Chlorine Eng Corp Ltd|Bonding of cation exchange membrane|
    US4604323A|1985-02-22|1986-08-05|E. I. Du Pont De Nemours And Company|Multilayer cation exchange membrane|
    DE4446675C2|1994-12-12|1997-10-23|Daramic Inc|Process for the repair of separator sheets for accumulators|
    GB0009506D0|2000-04-17|2000-06-07|Innogy Ltd|Ion exchange membrane|
    US6858045B2|2002-11-29|2005-02-22|Praxair Technology, Inc.|Method of manufacturing an electrolytic cell|
    US7043912B1|2004-12-27|2006-05-16|Utc Power, Llc|Apparatus for extracting exhaust heat from waste heat sources while preventing backflow and corrosion|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP6072580A|JPS6329695B2|1980-05-09|1980-05-09|
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