• 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:

    公开号:SU784786A3
    申请号:SU782605602
    申请日:1978-04-19
    公开日:1980-11-30
    发明作者:Густав Грот Вальтер；Джон Молнар Чарльз；Рафаэль Резник Пол
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

     Side chains in the form of ionic carboxyl groups and side chains in the form of ionic sulfonyl groups have high efficiency: in terms of current. Tek polymers are obtained by reduction of the initial fluorinated polymer containing sulfonyl groups P ,. The purpose of the invention is the creation of ion exchange materials with high current efficiency. The objectives are achieved by subjecting the starting fluorinated polymer with side chains containing groups of total Cr-cFa-SO M s / n) of formula IR where Rf is fluorine, chlorine or fluorinated alkyl radical C, -C M is a hydrogen atom, alkali metal or alkaline earth metal Am1 "onie: VA group, substituted ammonium group, including Quaternary ammonium or hydrazine group, including substituted hydrazine, and n is the valence of M, interaction with the oxidizing agent with the formation of fluorinated polymer, which has side dF - COOH (C / D) groups where M, n have specified e value Preferably, M in the starting fluorinated polymer is hydrogen, alkali or alkaline earth metal. More preferably, M in the starting polymer is hydrogen and n is 1. The starting fluorinated polymer can be used in any form, but preferably it is in the form of a film or membrane and has an ion exchange capacity of 0.5 to 1.6 meq / g. .When using the initial polymer in the form of a film or membrane, it is subjected to oxidation at least; One surface of the film to a depth of at least 200 A, so that the processing depth is less than half the thickness of the film or membrane. The conversion of the sulfonyl groups of the starting polymer leads to the formation of 10-90% of the carboxyl groups, preferably at least to 90% or, more preferably, to the formation of 95% of the carboxyl groups in the final fluorinated polymer. It is preferable to use B as the initial fluorinated polymer, containing in the side chain - CF-CFj-SOgX groups I R. where M is hydrazinium or substituted hydrazine, the product of the interaction of a fluorinated polymer with CF-CF2, -SO, X where X is fluorine or chlorine, with a compound of the formula where R and R. are the alkyl radical of the composition or, more preferably, hydrogen . Oxygen, chromic acid, permanganates, vanadates in acid solution, nitrous acid, and hypochlorites are used as oxidizing agents according to the invention. The term oxygen encompasses gas mixtures. which contain oxygen, such as air. Preferred oxidizing agents are oxygen, chromic acid, permanganates and vanadates, since the compounds listed are more effective. Oxygen can be used to oxidize the side chains defined above when M is hydrogen, i.e. when the functional group is free sulphinic acid. When using such an oxidizing agent, it is advisable to carry out the oxidation in the presence of a metal catalyst. It is also advisable to use elevated temperatures. At room temperature or near room temperature in the absence of a catalyst, although oxygen has little or no effect for several days, after three to four weeks there is a significant conversion to carboxyl groups. At higher temperatures, oxidation proceeds faster: for example, at a temperature of 50-60 ° C without a catalyst, a significant transformation into carboxyl groups occurs under the action of air for only a few days. In the case when oxygen is used as the oxidant, the polymer, film or membrane subjected to such treatment can be simply maintained in this gas, or contact with oxygen can be carried out in a liquid medium such as water. It is preferable to use a catalyst since this accelerates the reaction. Metals that can exist in more than one valence state can be used as a catalyst. (For present purposes, zero is considered as the valence state). For example, it has been found that salts of iron, vanadium, uranium cobalt, nickel, copper and manganese are effective. Other effective side-side oxidizing agents in cases where functional groups are in the form of free sulfinic acids or in the form of their alkaline earth metal salts include permanganates in either acid or base.
    chromic acid, vanadates in acidic medium, nitrous acid, and hypochlorites in alkaline medium. It should be borne in mind that when using such an oxidant, the polymer may either be in the form of the free acid or its salt, and that a mutual transition of the acid form or salt form may occur depending on the pH of the oxidizing medium used. Oxidation is usually carried out at temperatures above room temperature. The indicated oxidation can be carried out in media such as water, or in the presence of inorganic or organic acids, such as sulfuric acid, hydrochloric acid, acetic acid, etc.
    Also found that side. QF-CFj-50z H groups can be converted
    in CF-COOH group in boiling water or

    boiling organic or inorganic acids, for example formic acid, for a period of at least several hours. It can be assumed that oxidation with water can be carried out under such conditions. For the purposes of the present invention, oxidizing agents such as hydrogen peroxide and nitric acid are ineffective. There is an easy way to determine the extent to which the oxidizing agent is effective for carrying out the proposed process. To do this, it is only necessary to determine the presence or absence of characteristic bands in the infrared absorption spectrum of the product, corresponding to carboxylic acid groups, at about 1785 cm, or salts, at about 1680 cm.
    The ion exchange polymers of the invention have side chains that contain carboxyl groups bound to carbon atoms, having, in addition, at least one fluorine atom, and side chains that contain sulfonyl groups bound to carbon atoms that have at least one fluorine atom, as mentioned above.
    The ion exchange polymers of the present invention, which have side chains with carboxyl groups and side chains with sulfonyl groups, have properties that are inherent in ion exchange resins. When using a film or membrane as a separation device, separating the anodic chamber from the cathode in the electrolyzer, as, for example, in the electrolyzer to obtain chlorine and alkali, the polymer should have a total ion exchange capacity ranging from 0.5 to 1.6 meq / g, preferably , ranging from 0.8 to 1.2 mEq / g. When the value of the ion exchange ability
    below 0.5 meq / g, the electrical resistance becomes too high, and with an ion-exchange value, the ability to carry over 1.6 meq / g of mechanical properties deteriorates significantly, as excessive polymer swelling occurs.
    The initial fluorinated polymers are obtained from known compounds — fluorinated polymers with sulfonyl-halide groups.1
    0
    These polymeric compounds can be obtained by known methods from the corresponding fluorinated monomers.
    Preferred starting fluorinated polymers, as mentioned above, are obtained from known fluorinated polymers, which include side chains with | CF - CPg - groups,

    0 With a compound of formula Rj, where
    R and R, j are hydrogen or alkylE with 1 to 8 carbon atoms, preferably hydrogen. The preferred reducing agent is hydrazine, which
    5 is determined by its availability. Another effective compound is methyl hydrazine. Accordingly, the preferred reductants are those having the formula
    0 H, j N-NHR.
    Recovery can be carried out under various conditions. For example, it has been found that hydrazine is effective 1 when using
    5 as an anhydrous compound, as a hydrazine hydrate, as a 50% (by weight) solution in water or in a solution and other solutions, such as dimethyl sulfoxide. The reduction with hydrazine should preferably be carried out in the presence of an acid acceptor. The acid acceptor can be a tertiary amine, such as N-methylmorpholine, pyridine or triethylamine, or a metal hydroxide, such as potassium hydroxide or sodium hydroxide. The use of hydroxides or a tertiary amine is preferred because the sulphinoacid product and
    Hydrogen fluoride produced may give salts with a hydrazine reagent. Hydrates of oxides or tertiary amine form a salt with sulfinic acid and allow hydrazine to restore other sulfonyl halide groups.
    Hydrazine reduction is usually carried out at temperatures from above room temperature to about, although higher values
    0 temperatures can also be applied. By reducing the amount of water in the reaction medium, the reaction rate increases. The reaction rate is also higher when used as
    five
     dimethyl sulfoxide, as well as in the presence of hydroxide or Tppfi amine.
    After reduction with hydrazine, it is most advisable before carrying out the oxidation stage to polymer in order to remove excess hydrazine from it. At the same time, if it is necessary to obtain the polymer in the form of the free acid or its salt, it can be washed with acid or alkali. The choice of a particular kind of polymer can be determined by the particular type of OXYLITE used,
    The examples of the present invention, as mentioned above, can be in the form of films and membranes by the proposed method of 0.051-0.51 mm. Thicker films are preferable to achieve higher strength - but an increase in thickness is accompanied by an increase in electrical resistance.
    The term membranes denotes non-porous structures designed to separate chambers in electrolytic cells. Membranes can consist of layers of different materials, formed, for example, by surface modification of films or by lamination. In addition, the term membrane refers to structures containing a single layer on a substrate, such as a fabric that is immersed in a layer,
    The proposed method can produce films or membranes, in which the side chains are almost completely (i.e. 90% or more) or completely (i.e., up to about 99%) exist in carboxyl groups throughout the structure, e. also films and membranes, in which the side chains along the structure are in the form of carboxyl and sulfonyl groups, for example, from 10 to 90% of each type. The adjustment of these parameters is carried out during the recovery of the polymer precursor, which (possesses sulfonyl 1: Alohid groups., L9 nshodnogo polymer, which contains sulphinic acid groups. With or without competing reactions, which allow to obtain various products. For example, volume 3 In the case when 100% hydrazine is used as a reagents in the reduction reaction, the conversion to the functional sulfinic group and at the end of the condo to the carboxyl functional group can be It can be as high as 90-95%, and it can be assumed that the maximum conversion of the surface layers in the sulfine and carboxyl groups can reach 98 or 99%. When using a combination of hydrazine and hydroxide in a solvent such as water or dimethyl sulfoxide, some groups to the sulfinic form and hydrolysis of others to the sulfi acid group, does not change in the oxidation reaction, this causes the occurrence of carboxyl and sulfonyl groups in such relative amounts, which are determined by relative o.pichestvami hydrazine, water and hydroxide. The adjustment of the relative amounts of carboxyl and sulfonyl Edx functional groups can be carried out to some extent during the oxidation reaction. Some oxidizers, such as chromic acid and vanadates, will produce relatively large amounts of the original sulfo groups, while other oxidizers, such as hypochlorite. will give large quantities of the original sulfo groups.
    It also introduces BOSMO / KHIJIV to fabricate a membrane of the membrane, on the entire side of which the polymer has; the side chains are in the carboxyl form and the side chains are the IB sulfonyl form, and the other surface of the polymer is characterized by the presence of side chains that are completely in the sulfonyl form. In addition, : it is possible to manufacture films or membranes, both surfaces of which are polymer with side and g chains containing carboxyl form and with side chains containing sulfonyl 1: New form, and the inside layer has bare chains in sulfonyl form.
    In the case when the original polymer is modified top & on one surface and modify it from to; carboxyl groups, depth (the modified layer will usually be from 0, C1 to 80% of the film thickness. In the case: when both surfaces are modified; the depth of each modified layer is less than half the thickness of the structure, and as a rule it will be: leave 9.01-40% of the film thickness, the thickness of the modified layer containing carboxyl groups, will be at least 200 A. A convenient way of processing only one surface of the film or membrane is to give them the shape of a bag and sealing the hole, and processing only the inner or outer side of the membrane. In the case when only one surface is subjected to modification for the appearance of carboxyl groups in it, this surface in the electrolytic cells can be turned either to the anode or to the cathode, and in the case of electrolytic cells for production chlorine and alkali, it is usually an image to the cathode.
    It was found that when using fluorinated polymers of the type
    as described in the invention, containing side chains with carboxyl groups and side chains with sulfonyl groups, significant advantages are achieved in electrolytic cells for the production of chlorine and alkali with respect to current efficiency.
    Example 1. A film with a thickness of 0 mm from a copolymer of tetrafluoroethylene and fully fluorinated 3, b-diex-4-methyl-7-octenesulfonyl fluoride having an equivalent weight of 1100, immersed for 16 hours at room temperature in hydrazine hydrate, washed with water and immersed again; a 30 min at room temperature in a 5% solution of potassium hydroxide. The film is washed with water and immersed at room temperature in a mixture of 25 ml of OO acid ants and 5 ml of 37% hydrochloric acid in an oxygen atmosphere. After 5 and 60 hours at room temperature and then after another 2 hours at 70-80 ° C, the conversion to the carboxylic acid form in this medium was determined by infrared spectroscopy.
    The degree of conversion to the carboxylic acid form is further increased by heating the film (after washing with water) for 2 hours while in a mixture of 75% acetic acid, 3% concentrated sulfuric acid, 2% chromium trioxide and 20% water. The film is quenched with water and, for testing, kept in the electrolyzer for 2 hours at 70 ° C in a 10% solution of sodium hydroxide. An aqueous solution of sodium chloride was subjected to electrolysis at a current density of 0.31 L / cm. Received 35% MAON with a current efficiency of 91% and a voltage of 4.9 V.
    Example 2. About 1 mm film of copolymer of tetrafluoroethylene and exhaustively fluorinated 3,6-diXi-4-methyl-7-octenesulfonyl fluoride, having an equivalent weight of 1100, is immersed for 20 hours at room temperature in a mixture of 300 ml of dimethyl sulfoxide 100 ml of M of methylmorpholine and 80 85% hydrazine hydrate. The film is then washed with a dilute potassium hydroxide solution and water and immersed for three minutes at room temperature in a mixture of 200 ml of acetic acid, 10 ml of concentrated sulfuric acid, 1 g of vanadate ag monz, 1 g of vanadyl sulfate and 300 ml of water. Then the film is washed with water and maintained at room temperature for 6 days.
    After that, the film is transformed into the potassium salt form, for which it is kept for 30 minutes in a solution containing 13% potassium hydroxide and 30% dimethyl sulfoxide, and then washed with water.
    X-ray fluorescence showed that the potassium content in
    this moment is 0.96 S g-at / kg and sulfur 0.075 g, at / kg. This indicates that the content of carboxylate groups is 0.89 meq / g and the sufate groups is 0.075 meq / g.
    An aqueous solution of sodium chloride was electrolyzed at a current density of 0.31 A / cm-in the cell and using the specified film as a membrane.
    Get 35% NaOH current efficiency
    0 92% and voltage in the cell 4.9 V.
    Example 3. 0.1 mm film of copolymer of tetrafluoroethylene and exhaustively fluorinated 3,6-diox-4-methyl-7-octenesulfonyl fluoride ,,
    S having an equivalent weight of 1100, immersed for 30 hours at room temperature B 85% hydrazine hydrate (54% anhydrous hydrazine). The film is then washed with water and a dilute solution of potassium hydroxide. - Using infrared spectroscopy, it was found that this treatment leads to a virtually complete reduction of the sulphuryl groups to thionyl
    5 groups per vezh-depth of the plugs.
    Then the film is kept at 70 ° C for 17 hours in a solution containing 5% chromium trioxide and 50% / x-acid acid S water, rinsing with water and kept for 2 hours
    0 at 70 ° C in a 10% solution of sodium hydroxide in order to prepare a film for testing in a cell, using KtsU sodium chloride electrolyte and 3 ovac V.: -. - g; pi; current density 0.31 A /
    5 / cm-, and rszu; for one day, a 33% sodium oxide hydrate was obtained at a CPL with respect to the current and voltage in a cell of 4.1 V.
    P r and L er 4. Put in a cup
    0 in the form of footer OBKg: 0.1778 ml of a film of copolymer of tetrafluoroethylene and exhaustively fluorinated 3,6-diox-4-methyl-7-octenesulfonyl fluoride, having an equivalent weight of 1100, and pouring anhydrous hydrazine into the lining
    5 (95%), so that it makes contact only with the upper surface of the film. After two minutes at room temperature, the hydrazine is removed and the film is washed with water.
    The film is then immersed in 50 ml of glacial acetic acid and 1 to 25 ml of 20% sodium nitrite solution is added in separate portions and in portions over the course of one hour.
    5 The film was again blown out (with water. By etching the cross section with brilliant red 4G-mark Sevron R, it was shown that the reaction was wound to a depth of 0.05 mm.
    Unreacted SO. groups
    权利要求:
    Claims (2)
    [1]
    0 is hydrolyzed for 30 minutes at 90 ° C in a solution of potassium hydroxide hydrate (13%) in aqueous dimethyl sulfoxide (30%). The film is placed in an electrolytic cell to obtain chlorine and alkali, with which the film is set relative to the cathode solution on the side that Kotor was treated with hydrazine and oxidized. An aqueous solution of sodium chloride was electrolyzed at a density; current was 0.31 A / cm, resulting in a yield of 25% On OH with efficiency. 81% current and voltage in cell 4, 3 V. Example 5. A film with a thickness of 0.178 mm made from copolymer of tetrafluoroethylene and exhaustively fluorinated 3, b-diox-4-methyl-7-octenesulfonyl fluoride, having an equivalent weight of 1100, is folded and sealed in bag, leaving only a small opening for the introduction of reagents. 250 ml of dimethyl sulfoxide, 100 ml of N-methylmorpholine and 90 ml of hydrazine hydrate are poured into the bag and the film is held in this mixture at room temperature for 7 minutes. Then the mixture is poured out of the bag, rinsed with water, and a solution containing 10% KOH and 10% dimethyl sulfoxide is poured into it for an hour, then the bag is rinsed with water and then diluted with acetic acid. The bag is then opened, the film is cut and stained with a Sevron R 4G brilliant red 4G cut. It has been established that the reaction has gone to a depth of 0.6 ml (0.015 IVIM). The film is then treated for 30 minutes with a solution of 5 g of VOSO, 5 g of NH-.vVO and 5 ml of concentrated sulfuric acid in .3 l of water, washed with water and suspended for drying. After three days of exposure to air at room temperature, the film is treated with a solution containing 5% acetic acid, 2% and 2%, KbTSOxt in water for 1 hour. The film is then washed with water and strengthened in vacuo with a Teflon material, after which it is subjected to total hydrolysis for 20 minutes in a solution of KOH in aqueous dimethyl sulfaxide. The resulting membrane was evaluated in an electrolytic cell to obtain chlorine and alkali, with the surface being processed. tanna hydrazine and subjected to oxidation, was turned towards cathelite. Sodium oxide hydrate obtained concentrations of 31% by weight, with a current flow rate of 87% and a voltage in the electrolyzer of 5.8 V at a current density of 0.31 A / cm. Claim 1. Method for producing fluorinated ion-exchange carboxyl-containing polymers by reacting an initial fluorinated polymer containing side sulfonyl groups with a chemical reagent to convert part of the sulfonyl groups to carboxyl, characterized in that, for the purpose of simplification, the process technician for producing carboxyl-containing-X: olimers, fluorinated polymers containing - with F-CF - 50gM are used as the starting polymer (, / „groups in the side chains, where R | is fluorine, chlorine or perfluorinated alkyl The composition of G 1 Y M is a hydrogen atom, an alkali or alkaline earth metal, ammonium, including substituted or hydrazine, and n is the valence of M, and an oxidizing agent is used as a chemical reagent. 2. A method according to claim 1, characterized in that as the initial fluorinated polymer, use is made of the product of the interaction of the fluorinated polymer with sulfonyl groups of 50 dX, where X is fluorine or chlorine with hydrazine. 3. The method according to claim 1, characterized in that the initial fluorinated polymer is used in the form of a film or membrane with ion exchange. capacity 0.5-1.6 meq / g. 4. A method according to claim 3, characterized in that, at least one surface of the film or membrane is treated with an oxidizing agent to a depth of at least 200A, the surface of the film is treated with an oxidizing agent to a depth less than half the thickness of the film or membrane. 5. A method according to claim 1, characterized in that 10-95% of the sulfonyl groups are converted to carboxyl groups. 6. A method according to claim 4, characterized in that the surface treatment of the film with an oxidizing agent is carried out at a depth of less than half the thickness of the film or membrane. 7. Method according to paragraphs. 1 and 7, about one that means that about 95% of the sulfonyl groups are converted to carboxyl groups. 8. The method according to claim 1, characterized in that a polymer is used as the starting fluorinated polymer, in which M is hydrogen and n is 1 and oxygen is used as an oxidizing agent. 9. Method according to paragraphs. 1 and 8, which is due to the fact that the interaction of the starting polymer with oxygen is carried out in the presence of a catalytic amount of a variable-valence metal salt. 10. A method according to claim 9, characterized in that a salt of vanadium, iron, uranium, cobalt, nickel, copper or manganese is used as a catalyst. 11. The method according to claim 1, characterized by the fact that salts of manganese, vanadic or hypochlorous acid are used as the oxidizing agent, and. also chromic or nitrous acid. Sources of information taken into account in the examination. 1. US patent 3282875 cl. 260-296, published. 1966.
    [2]
    2. For number № 2503098/05 cl. From 08 F 8/04, 1976, according to which a decision was made to grant a patent to the USSR (prototype).
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    同族专利:
    公开号 | 公开日
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    CA1126443A|1982-06-22|
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    BR7802434A|1979-01-16|
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    引用文献:
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    US4200711A|1977-04-25|1980-04-29|Tokuyama Soda Kabushiki Kaisha|Process for preparing fluorine-containing polymers having carboxyl groups|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US78972677A| true| 1977-04-20|1977-04-20|
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