JP2002332376A - Method for recovering fluoropolymer - Google Patents
Method for recovering fluoropolymerInfo
- Publication number
- JP2002332376A JP2002332376A JP2002030881A JP2002030881A JP2002332376A JP 2002332376 A JP2002332376 A JP 2002332376A JP 2002030881 A JP2002030881 A JP 2002030881A JP 2002030881 A JP2002030881 A JP 2002030881A JP 2002332376 A JP2002332376 A JP 2002332376A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- solvent
- ion exchange
- exchange membrane
- inorganic particles
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、食塩電解などに使
用された含フッ素イオン交換膜から含フッ素ポリマーを
回収する方法に関する。The present invention relates to a method for recovering a fluorine-containing polymer from a fluorine-containing ion exchange membrane used for salt electrolysis or the like.
【０００２】[0002]
【従来の技術】含フッ素イオン交換膜は、食塩電解によ
り水酸化ナトリウムを製造する場合の電解槽の隔膜とし
て広く使用されている。このような含フッ素イオン交換
膜としては、カルボン酸基を有する含フッ素ポリマーの
フィルムとスルホン酸基を有する含フッ素ポリマーのフ
ィルムを２〜４層積層した複層型のイオン交換膜、この
複層型のイオン交換膜をポリテトラフルオロエチレン
（以下、ＰＴＦＥ）からなる織布で補強したもの等が用
いられている。2. Description of the Related Art Fluorine-containing ion exchange membranes are widely used as diaphragms in electrolytic cells when sodium hydroxide is produced by salt electrolysis. Examples of such a fluorine-containing ion exchange membrane include a multilayer ion exchange membrane in which two to four layers of a fluoropolymer film having a carboxylic acid group and a fluoropolymer film having a sulfonic acid group are laminated. A type of ion exchange membrane reinforced with a woven fabric made of polytetrafluoroethylene (hereinafter, PTFE) is used.
【０００３】また、電解中に発生するガスが膜表面に付
着することを防止し、電解電圧を低減させる目的から、
炭化ケイ素、酸化ジルコニウム等の無機粒子を複層型の
イオン交換膜の表面に被覆させたものが用いられてい
る。一方、イオン交換膜の表面には、電解中に鉄の酸化
物またはその水和物を主とする析出物（以下、表面析出
物という）が付着しやすい。In order to prevent the gas generated during electrolysis from adhering to the film surface and reduce the electrolysis voltage,
A material in which inorganic particles such as silicon carbide and zirconium oxide are coated on the surface of a multilayer ion exchange membrane is used. On the other hand, during electrolysis, a precipitate mainly composed of iron oxide or a hydrate thereof (hereinafter, referred to as a surface precipitate) easily adheres to the surface of the ion exchange membrane.
【０００４】従来、電解に使用されるイオン交換膜は性
能が低下した場合、電解槽より取り外され、廃棄物とし
て埋め立て等に使用され、処分されてきた。しかし、近
年、環境に与える影響から、イオン交換膜を構成する含
フッ素ポリマーを、イオン交換膜や燃料電池用の膜の材
料として回収し、再使用することが望まれている。Conventionally, ion exchange membranes used for electrolysis have been removed from the electrolytic cell when their performance has deteriorated, and used as landfills for waste disposal. However, in recent years, it has been desired to recover and reuse the fluorine-containing polymer constituting the ion-exchange membrane as a material for the ion-exchange membrane or the membrane for a fuel cell due to its influence on the environment.
【０００５】カルボン酸基を有する含フッ素ポリマー、
およびスルホン酸基を有する含フッ素ポリマーをイオン
交換膜から回収し、再使用するためには、両者を分別す
るだけでなく、上記イオン交換膜から前述した織布や無
機粒子を除く必要がある。A fluorine-containing polymer having a carboxylic acid group,
In order to recover and reuse the fluorinated polymer having a sulfonic acid group from the ion exchange membrane, it is necessary to not only separate the two but also remove the woven fabric and the inorganic particles from the ion exchange membrane.
【０００６】含フッ素イオン交換膜から含フッ素ポリマ
ーを回収する方法としては以下の方法が知られている。
例えば、カルボン酸基および／またはスルホン酸基を有
する２種以上の含フッ素ポリマー層からなる複層型含フ
ッ素イオン交換膜を、酸型またはアルカリ金属塩型に転
化した後、水溶性有機溶媒中に浸漬して各含フッ素ポリ
マーを溶出させ、その溶出液から各含フッ素ポリマーを
回収する方法（特公平３−１４８６０）、カルボン酸基
を有する含フッ素ポリマーとスルホン酸基を有する含フ
ッ素ポリマーからなる複層型イオン交換膜を、含フッ素
アルコール中に浸漬してスルホン酸基を有する含フッ素
ポリマーを溶出させる方法（特開２０００−８６８０
９）。The following method is known as a method for recovering a fluorine-containing polymer from a fluorine-containing ion exchange membrane.
For example, after converting a multi-layer type fluorinated ion-exchange membrane composed of two or more types of fluoropolymer layers having a carboxylic acid group and / or a sulfonic acid group into an acid type or an alkali metal salt type, it is added to a water-soluble organic solvent. To elute each fluorine-containing polymer by immersion in water and recover each fluorine-containing polymer from the eluate (Japanese Examined Patent Publication No. 3-14860), from a fluorine-containing polymer having a carboxylic acid group and a fluorine-containing polymer having a sulfonic acid group. A multi-layered ion exchange membrane is immersed in a fluorinated alcohol to elute a fluorinated polymer having a sulfonic acid group (Japanese Patent Laid-Open No. 2000-8680).
9).
【０００７】しかし、これらの方法においては、含フッ
素ポリマーを溶解した後、濾過して無機粒子を除去する
が、無機粒子が微粒子であるため、その除去が困難であ
り、得られる含フッ素ポリマーの純度が低く再利用が難
しい、含フッ素ポリマーの全量を溶解させるのに大量の
溶媒を必要とする等の問題がある。However, in these methods, after dissolving the fluoropolymer, the inorganic particles are removed by filtration. However, since the inorganic particles are fine particles, it is difficult to remove the inorganic particles. There are problems that the purity is low and it is difficult to reuse, and a large amount of solvent is required to dissolve the entire amount of the fluoropolymer.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、カルボン酸
基を有する含フッ素ポリマー、スルホン酸基を有する含
フッ素ポリマー、および表面に無機粒子を含有するイオ
ン交換膜から、無機粒子を除去し、カルボン酸基を有す
る含フッ素ポリマー、およびスルホン酸基を有する含フ
ッ素ポリマーを各々高純度で効率よく回収する方法の提
供を目的とする。SUMMARY OF THE INVENTION The present invention provides a method for removing inorganic particles from a fluorine-containing polymer having a carboxylic acid group, a fluorine-containing polymer having a sulfonic acid group, and an ion-exchange membrane containing inorganic particles on the surface. An object of the present invention is to provide a method for efficiently recovering a fluoropolymer having a carboxylic acid group and a fluoropolymer having a sulfonic acid group with high purity.
【０００９】[0009]
【課題を解決するための手段】本発明は、カルボン酸基
を有する含フッ素ポリマー（以下、Ｃポリマーとい
う）、およびスルホン酸基を有する含フッ素ポリマー
（以下、Ｓポリマーという）を含有し、表面に無機粒子
が付着したイオン交換膜を溶媒により膨潤させて表面の
無機粒子を除去した後、Ｓポリマーの良溶媒であり、か
つＣポリマーの貧溶媒である溶媒に接触させ、主として
Ｃポリマーからなる固形物とＳポリマーを溶解した溶液
とを得、これらを固液分離により回収することを特徴と
する含フッ素ポリマーの回収方法を提供する。The present invention comprises a fluorine-containing polymer having a carboxylic acid group (hereinafter referred to as C polymer) and a fluorine-containing polymer having a sulfonic acid group (hereinafter referred to as S polymer). After removing the inorganic particles on the surface by swelling the ion-exchange membrane with the inorganic particles adhered to the solvent, and then contacting with a solvent that is a good solvent for the S polymer and a poor solvent for the C polymer, mainly consisting of the C polymer A method for recovering a fluoropolymer, comprising obtaining a solution in which a solid and an S polymer are dissolved, and recovering the solution by solid-liquid separation.
【００１０】ここで、無機粒子とは、ガスが付着するの
を防ぐためにイオン交換膜の表面に付着させた炭化ケイ
素または酸化ジルコニウムなどの粒子だけでなく、表面
析出物等の粒子を含む。なお、本明細書中において、Ｃ
ポリマーは酸型だけでなく、カルボン酸基を有する含フ
ッ素ポリマーの一部または全部が塩型になっているもの
を含む。同様にＳポリマーは酸型だけでなく、スルホン
酸基を有する含フッ素ポリマーの一部または全部が塩型
になっているものを含む。Here, the inorganic particles include not only particles such as silicon carbide or zirconium oxide adhered to the surface of the ion exchange membrane in order to prevent gas from adhering, but also particles such as surface precipitates. In the present specification, C
The polymer includes not only the acid form but also a part of or the whole of the fluorine-containing polymer having a carboxylic acid group is in a salt form. Similarly, the S polymer includes not only the acid form but also a form in which a part or all of the fluorinated polymer having a sulfonic acid group is in a salt form.
【００１１】本発明によれば、イオン交換膜を溶媒で膨
潤させて、イオン交換膜表面に付着する無機粒子を分
離、除去した後、ＣポリマーおよびＳポリマーを回収す
ることにより、これらのポリマーを純度よく得ることが
できる。According to the present invention, the ion exchange membrane is swollen with a solvent to separate and remove the inorganic particles adhering to the surface of the ion exchange membrane, and then the C polymer and the S polymer are recovered. It can be obtained with high purity.
【００１２】[0012]
【発明の実施の形態】膨潤したイオン交換膜から無機粒
子を分離する方法としては以下の方法が挙げられる。 １）イオン交換膜を固定する。加熱還流、ポンプ循環等
の方法で溶媒を連続的に供給し、イオン交換膜に接触さ
せる。イオン交換膜が膨潤するにしたがい無機粒子がイ
オン交換膜から分離し、溶媒中へ分散する。無機粒子の
分離を促進させる目的から、溶媒をイオン交換膜に接触
させるときにイオン交換膜を振動させてもよい。BEST MODE FOR CARRYING OUT THE INVENTION As a method for separating inorganic particles from a swollen ion-exchange membrane, the following method can be mentioned. 1) Fix the ion exchange membrane. The solvent is continuously supplied by a method such as heating reflux and pump circulation, and is brought into contact with the ion exchange membrane. As the ion exchange membrane swells, the inorganic particles separate from the ion exchange membrane and disperse in the solvent. For the purpose of promoting the separation of the inorganic particles, the ion exchange membrane may be vibrated when the solvent is brought into contact with the ion exchange membrane.
【００１３】２）イオン交換膜を適当な大きさ、好まし
くは１〜３０ｃｍ角程度に裁断し、溶媒中に投入して撹
拌する。撹拌時間は５時間以上、特には２０時間以上が
好ましい。イオン交換膜が膨潤するにしたがい無機粒子
がイオン交換膜から分離し、溶媒中へ分散する。このと
き、膨潤を進行させる目的から、溶媒を加熱することが
好ましい。次いで、ふるいにかけ、ふるい上にイオン交
換膜を残し、無機粒子を分散した溶媒と分離する、また
は、溶媒中の無機粒子を沈降させ、除去した後、イオン
交換膜を抜き出す方法等により無機粒子を除去する。2) The ion-exchange membrane is cut into a suitable size, preferably about 1 to 30 cm square, put into a solvent and stirred. The stirring time is preferably at least 5 hours, particularly preferably at least 20 hours. As the ion exchange membrane swells, the inorganic particles separate from the ion exchange membrane and disperse in the solvent. At this time, it is preferable to heat the solvent for the purpose of promoting swelling. Next, sieving, leaving the ion-exchange membrane on the sieve, and separating the inorganic particles from the solvent in which the inorganic particles are dispersed, or by sedimenting the inorganic particles in the solvent and removing them, removing the inorganic particles by a method of extracting the ion-exchange membrane, etc. Remove.
【００１４】本発明においてイオン交換膜を膨潤させる
溶媒としては、ＣポリマーおよびＳポリマーの溶解度が
低いものが好ましい。具体的には水溶性の有機溶媒と水
との混合溶媒が好ましい。好ましい水溶性の有機溶媒と
しては、メタノール、エタノール、ｎ−プロパノール、
ｉ−プロパノール、ジオキサン、アセトン、スルホラ
ン、エチレングリコール類、プロピレングリコール類が
挙げられる。なかでも、溶媒の回収および再使用のしや
すさから、メタノール、エタノール、ｎ−プロパノー
ル、ｉ−プロパノール、アセトンが好ましく、特には取
扱いのしやすさからメタノールまたはエタノールが好ま
しい。In the present invention, the solvent for swelling the ion exchange membrane is preferably a solvent having low solubility of C polymer and S polymer. Specifically, a mixed solvent of a water-soluble organic solvent and water is preferable. Preferred water-soluble organic solvents include methanol, ethanol, n-propanol,
Examples include i-propanol, dioxane, acetone, sulfolane, ethylene glycols, and propylene glycols. Among them, methanol, ethanol, n-propanol, i-propanol, and acetone are preferred from the viewpoint of easy recovery and reuse of the solvent, and methanol or ethanol is particularly preferred from the viewpoint of easy handling.
【００１５】水溶性の有機溶媒と水との混合溶媒におけ
る水の含有割合は、水溶性の有機溶媒の種類、温度によ
り異なるが、５０質量％以上が好ましく、特には８０〜
９５質量％が好ましい。なお、特に好ましい有機溶媒と
水との混合溶媒は、エタノールと水との混合溶媒であっ
て、水の含有割合が６０〜９８質量％であるものであ
る。The content of water in a mixed solvent of a water-soluble organic solvent and water depends on the type and temperature of the water-soluble organic solvent, but is preferably 50% by mass or more, and particularly preferably 80 to 80% by mass.
95 mass% is preferred. A particularly preferred mixed solvent of an organic solvent and water is a mixed solvent of ethanol and water, and has a water content of 60 to 98% by mass.
【００１６】イオン交換膜を膨潤させるときの温度は、
溶媒等により異なるが、０〜１００℃が採用でき、特に
は１５〜５０℃が好ましい。温度が高すぎる場合は、Ｃ
ポリマーおよびＳポリマーの溶媒への溶解量が増え、Ｃ
ポリマーおよびＳポリマーの回収率が低下する。イオン
交換膜を膨潤させるときの圧力は常圧でも加圧でもよ
い。The temperature at which the ion exchange membrane swells is
Although it varies depending on the solvent and the like, 0 to 100 ° C can be adopted, and particularly preferably 15 to 50 ° C. If the temperature is too high,
The amount of polymer and S polymer dissolved in the solvent increases,
The recovery of polymer and S-polymer is reduced. The pressure for swelling the ion exchange membrane may be normal pressure or pressurization.
【００１７】また、食塩電解に用いられた後のイオン交
換膜においては、含フッ素ポリマーは、カルボン酸基を
有するものもスルホン酸基を有するものもほとんどがナ
トリウムと塩を形成している。したがって、本発明にお
いては、後の工程でＣポリマーとＳポリマーを効率よく
分離する目的から、イオン交換膜を膨潤させるときに酸
を添加し、ＣポリマーおよびＳポリマーを塩型から酸型
に変換するのが好ましい。Further, in the ion exchange membrane after being used for the salt electrolysis, most of the fluorine-containing polymers having a carboxylic acid group and those having a sulfonic acid group form a salt with sodium. Therefore, in the present invention, in order to efficiently separate the C polymer and the S polymer in a later step, an acid is added when the ion exchange membrane is swollen, and the C polymer and the S polymer are converted from the salt form to the acid form. Is preferred.
【００１８】このとき用いる酸としては、塩酸、硫酸、
リン酸、硝酸、酢酸等が好ましく、特には塩酸が好まし
い。また、塩のほとんどを中和するためには、酸の添加
量を、Ｃポリマー中の塩型イオン交換基とＳポリマー中
の塩型イオン交換基との合計に対して１当量以上とする
のが好ましい。一方、酸の添加量は前記塩型イオン交換
基の合計に対して１０当量以下とするのが好ましい。ま
た、使用する酸の好ましい濃度は、酸の種類により異な
るが、０．５〜２０質量％である。The acid used at this time is hydrochloric acid, sulfuric acid,
Phosphoric acid, nitric acid, acetic acid and the like are preferred, and hydrochloric acid is particularly preferred. In order to neutralize most of the salts, the amount of the acid to be added is at least 1 equivalent to the total of the salt-type ion exchange groups in the C polymer and the salt-type ion exchange groups in the S polymer. Is preferred. On the other hand, the addition amount of the acid is preferably 10 equivalents or less based on the total of the salt-type ion exchange groups. The preferred concentration of the acid used depends on the type of the acid, but is 0.5 to 20% by mass.
【００１９】本発明においては、膨潤させたイオン交換
膜をＳポリマーの良溶媒であり、かつＣポリマーの貧溶
媒である溶媒（以下、分離溶媒という）に接触させて、
主としてＣポリマーからなる固形物とＳポリマーを溶解
した溶液とに分離し、回収する。In the present invention, the swollen ion exchange membrane is brought into contact with a solvent that is a good solvent for the S polymer and a poor solvent for the C polymer (hereinafter referred to as a separation solvent),
It is separated and recovered into a solid mainly composed of C polymer and a solution in which S polymer is dissolved.
【００２０】分離溶媒としては、Ｓポリマーの溶解度が
Ｃポリマーの溶解度の１０倍以上であるものが好まし
く、特には３０倍以上であるものが好ましい。具体的に
は、エタノール、メタノール、水の含有割合が４０質量
％以下のエタノール水溶液、水の含有割合が４０質量％
以下のメタノール水溶液が好ましく、特にはエタノール
が好ましい。なお、分離溶媒の種類のみならず、温度や
圧力を制御することにより溶解度の調整を行ってもよ
い。As the separation solvent, a solvent having a solubility of S polymer of 10 times or more as high as that of C polymer is preferable, and a solvent having a solubility of 30 times or more is particularly preferable. Specifically, ethanol, methanol, and an aqueous ethanol solution having a water content of 40% by mass or less, and a water content of 40% by mass.
The following aqueous methanol solutions are preferred, and ethanol is particularly preferred. The solubility may be adjusted by controlling not only the type of the separation solvent but also the temperature and pressure.
【００２１】本発明の含フッ素ポリマーの回収方法は、
ＣポリマーおよびＳポリマーを含有する食塩電解用のイ
オン交換膜からＣポリマーおよびＳポリマーを回収する
のに適している。The method for recovering a fluorine-containing polymer according to the present invention comprises:
It is suitable for recovering C polymer and S polymer from an ion exchange membrane for salt electrolysis containing C polymer and S polymer.
【００２２】上記食塩電解用のイオン交換膜のＣポリマ
ーとしては、テトラフルオロエチレンと、カルボン酸基
を有するパーフルオロビニルエーテルとの共重合体から
なり、イオン交換容量が０．８〜１．９ミリ当量／ｇ乾
燥樹脂であるものが挙げられる。上記共重合体として
は、テトラフルオロエチレンとカルボン酸エステル基を
有するパーフルオロビニルエーテルとの共重合体を前駆
体とし、これを加水分解して得られるものが好ましい。
ここで、カルボン酸エステル基を有するパーフルオロビ
ニルエーテルとしては、一般式ＣＦ２＝ＣＦ−（ＯＣＦ
２ＣＦＸ）ｐ−（Ｏ）ｑ−（ＣＦ２）ｒ−ＣＯ２ＣＨ３
（式中、ｐ＝０〜３の整数、ｑは０または１、ｐ＋ｑ≧
１、ｒは０〜１２の整数であり、Ｘは−Ｆまたは−ＣＦ
３である。）で示されるものが好ましく、特には以下に
示すものが好ましい。 ＣＦ2＝ＣＦＯＣＦ2ＣＦ2ＣＯ2ＣＨ3、 ＣＦ2＝ＣＦＯＣＦ2ＣＦ2ＣＦ2ＣＯ2ＣＨ3、 ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＦ2ＣＯ2Ｃ
Ｈ3。The C polymer of the ion exchange membrane for salt electrolysis is a copolymer of tetrafluoroethylene and perfluorovinyl ether having a carboxylic acid group, and has an ion exchange capacity of 0.8 to 1.9 mm. Equivalent / g dry resin. As the above copolymer, a copolymer obtained by using a copolymer of tetrafluoroethylene and a perfluorovinyl ether having a carboxylic acid ester group as a precursor and hydrolyzing the precursor is preferable.
Here, as the perfluorovinyl ether having a carboxylic acid ester group, a general formula CF 2 ＣＦCF— (OCF)
2 CFX) p- (O) q- (CF 2 ) r -CO 2 CH 3
(Where p is an integer of 0 to 3, q is 0 or 1, p + q ≧
1, r is an integer of 0 to 12, and X is -F or -CF
3 . ) Are preferable, and particularly those shown below are preferable. CF 2 = CFOCF 2 CF 2 CO 2 CH 3, CF 2 = CFOCF 2 CF 2 CF 2 CO 2 CH 3, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 CO 2 C
H 3.
【００２３】また、前駆体としてはテトラフルオロエチ
レン、カルボン酸エステル基を有するパーフルオロビニ
ルエーテルとともに、さらに以下に示すパーフルオロビ
ニルエーテルを重合させてなる３元系の共重合体も好ま
しい。 ＣＦ2＝ＣＦＯＣＦ2ＣＦ2ＣＦ3、 ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＦ2ＣＦ3。As the precursor, a terpolymer obtained by polymerizing perfluorovinyl ether shown below together with tetrafluoroethylene and perfluorovinyl ether having a carboxylic acid ester group is also preferable. CF 2 = CFOCF 2 CF 2 CF 3, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 CF 3.
【００２４】また、上記食塩電解用のイオン交換膜のＳ
ポリマーとしては、テトラフルオロエチレンと、スルホ
ン酸基を有するパーフルオロビニルエーテルとの共重合
体であって、イオン交換容量が０．８〜１．３ミリ当量
／ｇ乾燥樹脂であるイオン交換膜が挙げられる。上記共
重合体としては、テトラフルオロエチレンと、側鎖にス
ルホニルフルオライド基を有するパーフルオロビニルエ
ーテルとの共重合体を前駆体とし、これを加水分解して
得られるものが好ましい。ここで、スルホニルフルオラ
イド基を有するパーフルオロビニルエーテルとしては、
一般式ＣＦ２＝ＣＦ−（ＯＣＦ２ＣＦＺ）ｓ−（Ｏ）ｔ
−（ＣＦ２）ｕ−ＳＯ２Ｆ（式中、ｓ＝０〜３の整数、
ｔは０または１、ｓ＋ｔ≧１、ｕは０〜１２の整数であ
り、Ｚは−Ｆまたは−ＣＦ３である。）で示されるもの
が好ましく、特には以下に示すものが好ましい。 ＣＦ2＝ＣＦＯＣＦ2ＣＦ2ＳＯ2Ｆ、 ＣＦ2＝ＣＦＯＣＦ2ＣＦ（ＣＦ3）ＯＣＦ2ＣＦ2ＳＯ
2Ｆ。Further, the S of the ion exchange membrane for salt electrolysis
Examples of the polymer include an ion exchange membrane which is a copolymer of tetrafluoroethylene and a perfluorovinyl ether having a sulfonic acid group, and has an ion exchange capacity of 0.8 to 1.3 meq / g dry resin. Can be As the above copolymer, a copolymer obtained by using a copolymer of tetrafluoroethylene and a perfluorovinyl ether having a sulfonyl fluoride group in a side chain as a precursor and hydrolyzing the precursor is preferable. Here, as the perfluorovinyl ether having a sulfonyl fluoride group,
Formula CF 2 = CF- (OCF 2 CFZ ) s - (O) t
— (CF 2 ) u —SO 2 F (where s is an integer of 0 to 3,
t is 0 or 1, s + t ≧ 1, u is an integer of 0 to 12, and Z is —F or —CF 3 . ) Are preferable, and particularly those shown below are preferable. CF 2 = CFOCF 2 CF 2 SO 2 F, CF 2 = CFOCF 2 CF (CF 3 ) OCF 2 CF 2 SO
2 F.
【００２５】また、本発明においてはイオン交換膜がＰ
ＴＦＥからなる織布等の補強材と積層されている場合
は、補強材を、無機粒子を除去する際に除去してもよ
く、別途除去工程を設けて除去してもよい。In the present invention, the ion exchange membrane is made of P
When laminated with a reinforcing material such as a woven fabric made of TFE, the reinforcing material may be removed when removing the inorganic particles, or may be removed by providing a separate removing step.
【００２６】本発明によれば、ＣポリマーおよびＳポリ
マーは、いずれも純度が９０質量％以上、好ましくは９
５質量％以上で回収できる。このように、Ｃポリマーお
よびＳポリマーを、それぞれ高純度で回収できるので、
回収後、精製することなく再利用することも可能であ
る。ただし、用途によりさらなる純度の向上が必要な場
合は精製を行う。精製の方法としては、Ｃポリマーおよ
びＳポリマーとも、メタノール等のアルコール中で硫酸
存在下、加熱処理し、生成するＣポリマーのエステル体
等を取り除く方法が好ましい。According to the present invention, the C polymer and the S polymer each have a purity of 90% by mass or more, preferably 9% by mass.
It can be recovered at 5% by mass or more. As described above, since the C polymer and the S polymer can be respectively recovered with high purity,
After recovery, it can be reused without purification. However, if further improvement in purity is required depending on the application, purification is performed. As a purification method, a method is preferred in which both the C polymer and the S polymer are subjected to a heat treatment in an alcohol such as methanol in the presence of sulfuric acid to remove the resulting C polymer ester.
【００２７】本発明で回収されるＣポリマーは燃料電池
用の膜材料、食塩電解用のイオン交換膜の材料として再
使用できる。Ｓポリマーは燃料電池の膜材料、食塩電解
用のイオン交換膜の材料、フッ素樹脂系繊維の材料とし
て使用できる。本発明で回収される各ポリマーは無機粒
子の含有量が低いことから、特には、燃料電池用の膜材
料等の電子材料用途に好適である。The C polymer recovered in the present invention can be reused as a membrane material for a fuel cell and a material for an ion exchange membrane for salt electrolysis. S-polymer can be used as a membrane material for fuel cells, a material for ion exchange membranes for salt electrolysis, and a material for fluororesin fibers. Since each polymer recovered in the present invention has a low content of inorganic particles, it is particularly suitable for use in electronic materials such as membrane materials for fuel cells.
【００２８】本発明の含フッ素ポリマーの回収方法の具
体例は次のようになる。無機粒子およびＰＴＦＥの織布
を含むイオン交換膜を裁断したものを酸溶液、例えば１
０質量％の塩酸水溶液とエタノールとの混合溶液（体積
比：１０質量％の塩酸水溶液／エタノール＝９０％／１
０％）で処理する。次いで、ふるいで濾過を行い、得ら
れる濾物を水等の洗浄液で洗い無機粒子を除去する（濾
物がポリマー成分であり、濾液中に無機粒子が分散す
る）。濾物を分離溶媒、例えばエタノールに接触させ、
Ｃポリマーを主成分とする固形物と、Ｓポリマーを溶解
した溶液とに分離させる。Ｃポリマーを主成分とする固
形物は、メタノールなどの溶媒で溶解させ、濾過により
ＰＴＦＥの織布を分離、除去する。A specific example of the method for recovering a fluoropolymer of the present invention is as follows. An ion-exchange membrane containing inorganic particles and a PTFE woven cloth is cut into an acid solution such as 1
A mixed solution of 0 mass% hydrochloric acid aqueous solution and ethanol (volume ratio: 10 mass% hydrochloric acid aqueous solution / ethanol = 90% / 1
0%). Next, the mixture is filtered through a sieve, and the obtained residue is washed with a washing liquid such as water to remove inorganic particles (the residue is a polymer component, and the inorganic particles are dispersed in the filtrate). The filtrate is contacted with a separation solvent, for example, ethanol,
Separate into a solid containing C polymer as a main component and a solution in which S polymer is dissolved. The solid containing the C polymer as a main component is dissolved in a solvent such as methanol, and the PTFE woven fabric is separated and removed by filtration.
【００２９】[0029]
【実施例】以下に本発明の実施例（例１〜３）および比
較例（例４）を説明する。 [例１] イオン交換膜として、Ｃポリマーからなる膜と、Ｓポリ
マーからなる膜と、ＰＴＦＥからなる織布とが積層さ
れ、表面に無機粒子が付着したイオン交換膜であり、食
塩電解に使用したものを用意した。Ｃポリマーは、テト
ラフルオロエチレンとカルボン酸基を有するパーフルオ
ロビニルエーテルとの共重合体のナトリウム塩であり、
イオン交換容量が１．８ミリ当量／ｇ乾燥樹脂である。
Ｓポリマーはテトラフルオロエチレンとスルホン酸基を
有するパーフルオロビニルエーテルとの共重合体のナト
リウム塩であって、イオン交換容量が１．１ミリ当量／
ｇ乾燥樹脂である。EXAMPLES Examples of the present invention (Examples 1 to 3) and comparative examples (Example 4) will be described below. [Example 1] An ion exchange membrane in which a membrane made of a C polymer, a membrane made of an S polymer, and a woven fabric made of PTFE are laminated, and inorganic particles adhere to the surface, and are used for salt electrolysis. I prepared something. C polymer is a sodium salt of a copolymer of tetrafluoroethylene and perfluorovinyl ether having a carboxylic acid group,
The ion exchange capacity is 1.8 meq / g dry resin.
The S polymer is a sodium salt of a copolymer of tetrafluoroethylene and a perfluorovinyl ether having a sulfonic acid group, and has an ion exchange capacity of 1.1 meq /
g dry resin.
【００３０】冷却器、撹拌機を備えた５００ｍｌフラス
コに、１０質量％塩酸水溶液１８０ｇ、エタノール２０
ｇを入れ、上記イオン交換膜を２ｃｍ角に裁断したもの
９．０３ｇ（Ｃポリマー：７．５０ｇ、Ｓポリマー：
０．８６ｇ、織布：０．５４ｇ、炭化ケイ素：０．０３
ｇ、酸化ジルコニウム：０．０４ｇ、表面析出物（鉄元
素換算）：０．０６ｇ）を添加した。２０℃で１５時間
撹拌した後、１０メッシュのふるい（井内盛栄堂製：以
下同じ）で濾過を行った。得られた固体の濾物と水２０
０ｇを５００ｍｌフラスコに入れ、２０℃で３０分撹拌
後、１０メッシュのふるいで濾過を行った。この濾物と
水とを混合、撹拌した後、濾過を行う操作を３回繰り返
し、無機粒子を除去した。In a 500 ml flask equipped with a condenser and a stirrer, 180 g of a 10% by mass aqueous hydrochloric acid solution, 20 g of ethanol
g, and the above ion-exchange membrane was cut into 2 cm square 9.03 g (C polymer: 7.50 g, S polymer:
0.86 g, woven fabric: 0.54 g, silicon carbide: 0.03
g, zirconium oxide: 0.04 g, and surface precipitates (in terms of iron element): 0.06 g). After stirring at 20 ° C. for 15 hours, the mixture was filtered through a 10-mesh sieve (manufactured by Iuchi Seieido; the same applies hereinafter). The resulting solid residue and water 20
0 g was put in a 500 ml flask, stirred at 20 ° C. for 30 minutes, and filtered through a 10-mesh sieve. The operation of mixing and stirring the residue and water was repeated three times to remove inorganic particles.
【００３１】無機粒子が除去された濾物とエタノール２
００ｇを５００ｍｌフラスコに入れ、６０℃で１５時間
還流した後、１０メッシュのふるいで濾過を行い、Ｃポ
リマーおよびＰＴＦＥからなる織布を濾物として、Ｓポ
リマーが溶解したエタノール溶液を濾液として取り出し
た。ここで、６０℃におけるエタノールに対するＳポリ
マーの溶解度は、該エタノールに対するＣポリマーの溶
解度の５０倍である。The filtrate from which the inorganic particles have been removed and ethanol 2
After placing 00 g in a 500 ml flask and refluxing at 60 ° C. for 15 hours, the solution was filtered through a 10-mesh sieve, and a woven fabric composed of C polymer and PTFE was taken out as a filter, and an ethanol solution in which S polymer was dissolved was taken out as a filtrate. . Here, the solubility of the S polymer in ethanol at 60 ° C. is 50 times the solubility of the C polymer in ethanol.
【００３２】次いで、得られた濾液を４０００ｒｐｍで
３０分間遠心分離し、その上澄み液を孔径０．３μｍの
濾紙（東洋濾紙製：以下同じ）で濾過を行った後、エタ
ノールを留去し、無色透明な酸型のＳポリマーを収率６
９．５％で得た。Next, the obtained filtrate was centrifuged at 4000 rpm for 30 minutes, and the supernatant was filtered through a filter paper having a pore diameter of 0.3 μm (manufactured by Toyo Roshi Kaisha; the same applies hereinafter). Transparent acid type S-polymer yield 6
Obtained at 9.5%.
【００３３】また、Ｃポリマー、およびＰＴＦＥからな
る織布を含む濾物とメタノール２００ｇをフラスコに入
れ、６０℃で１５時間還流した後、１０メッシュのふる
いで濾過を行い、ＰＴＦＥからなる織布を除去した。次
いで、濾液を４０００ｒｐｍで３０分間遠心分離し、そ
の上澄み液を孔径０．３μｍの濾紙で濾過を行った後、
メタノールを留去し、無色透明な酸型のＣポリマーを収
率８７．４％で得た。Further, a filtered material containing a woven fabric made of the C polymer and PTFE and 200 g of methanol were placed in a flask, refluxed at 60 ° C. for 15 hours, and then filtered through a 10-mesh sieve to obtain a woven fabric made of PTFE. Removed. Next, the filtrate was centrifuged at 4000 rpm for 30 minutes, and the supernatant was filtered through filter paper having a pore size of 0.3 μm.
The methanol was distilled off to obtain a colorless and transparent acid-form C polymer in a yield of 87.4%.
【００３４】得られたＣポリマーおよびＳポリマーのそ
れぞれについて、炭化ケイ素、酸化ジルコニウムおよび
表面析出物（鉄元素換算）の含有量をＩＣＰ（高周波誘
導結合プラズマ発光分光分析）により測定したところ、
すべて１０ｐｐｍ以下であった。また19Ｆ−ＮＭＲ（超
電導核磁気共鳴分析）よりポリマー純度を測定したとこ
ろ、Ｃポリマーの純度は９５％であり、Ｓポリマーの純
度は９５％であった。For each of the obtained C polymer and S polymer, the contents of silicon carbide, zirconium oxide and surface precipitates (in terms of iron element) were measured by ICP (high frequency inductively coupled plasma emission spectroscopy).
All were below 10 ppm. Further, when the polymer purity was measured by 19 F-NMR (superconducting nuclear magnetic resonance analysis), the purity of the C polymer was 95% and the purity of the S polymer was 95%.
【００３５】また、以下のようにしてＣポリマーをさら
に高純度化した。冷却器、撹拌機を備えた５０ｍｌフラ
スコに、得られたＣポリマー０．４ｇ、メタノール１
９．６ｇおよび濃硫酸０．０２ｇを入れ、約５８℃で６
時間、撹拌下、還流させた。冷却後、孔径３μｍのメン
ブレンフィルターで濾過を行い、濾物として得たＣポリ
マーを19Ｆ−ＮＭＲで分析したところ、純度は９９％で
あった。The C polymer was further purified as follows. In a 50 ml flask equipped with a condenser and a stirrer, 0.4 g of the obtained C polymer, methanol 1
Add 9.6 g and 0.02 g of concentrated sulfuric acid,
The mixture was refluxed for a period of time with stirring. After cooling, the solution was filtered through a membrane filter having a pore size of 3 μm, and the C polymer obtained as a filtrate was analyzed by 19 F-NMR. As a result, the purity was 99%.
【００３６】また、以下のようにしてＳポリマーをさら
に高純度化した。冷却器、撹拌機を備えた５０ｍｌフラ
スコに、得られたＳポリマー０．４ｇ、メタノール１
９．６ｇおよび濃硫酸０．０２ｇを入れ、約５８℃で６
時間、撹拌下、還流させた。冷却後、孔径３μｍのメン
ブレンフィルターで濾過を行い、濾液として得たＳポリ
マーのメタノール溶液を19Ｆ−ＮＭＲで分析したとこ
ろ、純度は９９％であった。The S-polymer was further purified as follows. In a 50 ml flask equipped with a condenser and a stirrer, 0.4 g of the obtained S-polymer and methanol 1
Add 9.6 g and 0.02 g of concentrated sulfuric acid,
The mixture was refluxed for a period of time with stirring. After cooling, the solution was filtered through a membrane filter having a pore size of 3 μm, and the methanol solution of S polymer obtained as a filtrate was analyzed by 19 F-NMR. As a result, the purity was 99%.
【００３７】［例２］１０質量％の塩酸水溶液のかわり
に水を用いた以外は、例１と同様にしてイオン交換膜か
ら無機粒子を除去した。次いで、例１と同様の操作を行
い、無色透明のナトリウム塩型のＳポリマーを収率５
７．４％で得、無色透明のナトリウム塩型のＣポリマー
を収率７６．４％で得た。Example 2 Inorganic particles were removed from the ion exchange membrane in the same manner as in Example 1 except that water was used instead of the 10% by mass aqueous hydrochloric acid solution. Next, the same operation as in Example 1 was performed to obtain a colorless and transparent sodium salt type S polymer in a yield of 5%.
Thus, a colorless and transparent sodium salt type C polymer was obtained at a yield of 76.4%.
【００３８】得られたＳポリマーおよびＣポリマーのそ
れぞれについて、炭化ケイ素、酸化ジルコニウム、表面
析出物（鉄元素換算）の含有量をＩＣＰにて測定したと
ころ、すべて１０ｐｐｍ以下であった。また19Ｆ−ＮＭ
Ｒより純度を測定したところ、Ｓポリマーの純度は９０
％であり、Ｃポリマーの純度は９５％であった。The content of silicon carbide, zirconium oxide, and surface precipitates (in terms of iron element) of each of the obtained S polymer and C polymer was measured by ICP and found to be all 10 ppm or less. Also 19 F-NM
When the purity was measured from R, the purity of the S polymer was 90%.
% And the purity of the C polymer was 95%.
【００３９】［例３］イオン交換膜として以下の膜９．
３４ｇを用いた以外は例２と同様にして無色透明なナト
リウム塩型のＳポリマーを収率７６．５％で得、無色透
明なナトリウム塩型のＣポリマーを収率５３．４％で得
た。Example 3 The following membrane as an ion exchange membrane 9.
A colorless and transparent sodium salt type S polymer was obtained in a yield of 76.5% in the same manner as in Example 2 except that 34 g was used, and a colorless and transparent sodium salt type C polymer was obtained in a yield of 53.4%. .
【００４０】使用したイオン交換膜は、Ｃポリマーから
なる膜２．２０ｇと、Ｓポリマー（Ｓポリマーａとい
う）からなる膜４．４０ｇと、別のＳポリマー（Ｓポリ
マーｂという）からなる膜１．８９ｇと、ＰＴＦＥから
なる織布０．５８ｇとが積層され、無機粒子（酸化ジル
コニウム０．１４ｇおよび表面析出物（鉄元素換算）
０．１３ｇ）を含有するイオン交換膜であり、食塩電解
に使用したものである。The ion-exchange membrane used was 2.20 g of a membrane made of a C polymer, 4.40 g of a membrane made of an S polymer (S polymer a), and a membrane 1 made of another S polymer (S polymer b). .89 g and a woven fabric made of PTFE 0.58 g were laminated, and inorganic particles (0.14 g of zirconium oxide and surface precipitates (in terms of iron element))
0.13 g), which was used for salt electrolysis.
【００４１】Ｃポリマーは、テトラフルオロエチレンと
カルボン酸基を有するパーフルオロビニルエーテルとの
共重合体のナトリウム塩であって、イオン交換容量が
１．０ミリ当量／ｇ乾燥樹脂であるもの、Ｓポリマーａ
はテトラフルオロエチレンとスルホン酸基を有するパー
フルオロビニルエーテルとの共重合体のナトリウム塩で
あって、イオン交換容量が１．１ミリ当量／ｇ乾燥樹脂
であるもの、Ｓポリマーｂはテトラフルオロエチレンと
スルホン酸基を有するパーフルオロビニルエーテルとの
共重合体のナトリウム塩であって、イオン交換容量が
１．０ミリ当量／ｇ乾燥樹脂であるものである。The C polymer is a sodium salt of a copolymer of tetrafluoroethylene and a perfluorovinyl ether having a carboxylic acid group, the ion exchange capacity of which is 1.0 meq / g dry resin, the S polymer a
Is a sodium salt of a copolymer of tetrafluoroethylene and a perfluorovinyl ether having a sulfonic acid group, having an ion exchange capacity of 1.1 meq / g dry resin. A sodium salt of a copolymer with a perfluorovinyl ether having a sulfonic acid group, having an ion exchange capacity of 1.0 meq / g dry resin.
【００４２】得られたＳポリマーおよびＣポリマーのそ
れぞれについて、酸化ジルコニウムおよび表面析出物
（鉄元素換算）の含有量をＩＣＰにて測定したところ、
すべて１０ｐｐｍ以下であった。また19Ｆ−ＮＭＲより
ポリマー純度を測定したところ、Ｓポリマーの純度は９
４％であり、Ｃポリマーの純度は９０％であった。For each of the obtained S polymer and C polymer, the contents of zirconium oxide and surface precipitates (in terms of iron element) were measured by ICP.
All were below 10 ppm. When the polymer purity was measured by 19 F-NMR, the purity of the S polymer was 9
4%, and the purity of the C polymer was 90%.
【００４３】［例４］例３で用いたのと同じイオン交換
膜を用い、例３と同様にしてイオン交換膜から無機粒子
を除去した。これにメタノール２００ｇを加え、６０℃
で１５時間還流した後、１０メッシュのふるいで濾過を
行い、ＰＴＦＥからなる織布を濾物として、Ｃポリマー
およびＳポリマーの混合溶液を濾液として得た。この濾
液を４０００ｒｐｍで３０分間遠心分離し、その上澄み
液を孔径０．３μｍの濾紙で濾過を行った後メタノール
を留去し、ＣポリマーとＳポリマーの混合物を固体とし
て得た。この混合物とエタノール２００ｇをフラスコに
入れ、６０℃で１５時間還流した後、孔径０．３μｍの
濾紙で濾過を行い、濾物としてナトリウム塩型のＣポリ
マーを収率５１．１％で得た。さらに濾液中のエタノー
ルを留去してナトリウム塩型のＳポリマーを収率７１．
３％で得た。Example 4 The same ion exchange membrane as used in Example 3 was used, and inorganic particles were removed from the ion exchange membrane in the same manner as in Example 3. 200 g of methanol was added to this,
After refluxing for 15 hours, filtration was performed with a 10-mesh sieve to obtain a mixed solution of C polymer and S polymer as a filtrate using a woven cloth made of PTFE as a filter substance. The filtrate was centrifuged at 4000 rpm for 30 minutes. The supernatant was filtered through a filter paper having a pore size of 0.3 μm, and then methanol was distilled off to obtain a mixture of C polymer and S polymer as a solid. This mixture and 200 g of ethanol were placed in a flask, refluxed at 60 ° C. for 15 hours, and then filtered through a filter paper having a pore size of 0.3 μm to obtain a sodium salt type C polymer as a filtered product in a yield of 51.1%. Further, ethanol in the filtrate was distilled off to obtain a sodium salt type S polymer in a yield of 71.
Obtained at 3%.
【００４４】ＳポリマーおよびＣポリマーのそれぞれに
ついて、酸化ジルコニウム、表面析出物（鉄元素換算）
の含有量をＩＣＰにて測定したところ、すべて１０ｐｐ
ｍ以下であった。また、19Ｆ−ＮＭＲよりポリマー純度
を測定したところ、Ｓポリマーの純度は９３％であり、
Ｃポリマーの純度は８２％であった。For each of the S polymer and the C polymer, zirconium oxide and surface precipitate (in terms of iron element)
Was measured by ICP.
m or less. Further, when the polymer purity was measured by 19 F-NMR, the purity of the S polymer was 93%,
The purity of the C polymer was 82%.
【００４５】[0045]
【発明の効果】本発明により、使用後の含フッ素イオン
交換膜中の含フッ素ポリマーが効率よく、簡便に回収で
きる。上記含フッ素ポリマーのリサイクル工程が確立で
き、廃棄物の低減が図られる。According to the present invention, the fluorinated polymer in the fluorinated ion exchange membrane after use can be efficiently and simply recovered. A process for recycling the above fluoropolymer can be established, and waste can be reduced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 深津 隆 神奈川県茅ヶ崎市茅ヶ崎３丁目２番10号 セイミケミカル株式会社内 (72)発明者 徳倉 良太 神奈川県茅ヶ崎市茅ヶ崎３丁目２番10号 セイミケミカル株式会社内 Ｆターム(参考） 4F301 AA18 BF11 BF25 BF26 BF27 BF32 CA09 CA12 CA33 CA53 CA65 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Takashi Fukatsu, Inventor 3-2-1-10 Chigasaki, Chigasaki-shi, Kanagawa Prefecture Inside Seimi Chemical Co., Ltd. (72) Ryota Tokukura 3-2-1-10 Chigasaki, Chigasaki-shi, Kanagawa Prefecture Seimi Chemical F term (reference) 4F301 AA18 BF11 BF25 BF26 BF27 BF32 CA09 CA12 CA33 CA53 CA65
Claims (6)
（以下、Ｃポリマーという）、およびスルホン酸基を有
する含フッ素ポリマー（以下、Ｓポリマーという）を含
有し、表面に無機粒子が付着したイオン交換膜を溶媒に
より膨潤させて表面の無機粒子を除去した後、Ｓポリマ
ーの良溶媒であり、かつＣポリマーの貧溶媒である溶媒
に接触させ、主としてＣポリマーからなる固形物とＳポ
リマーを溶解した溶液とを得、これらを固液分離により
回収することを特徴とする含フッ素ポリマーの回収方
法。1. An ion-exchange resin containing a fluorinated polymer having a carboxylic acid group (hereinafter, referred to as C polymer) and a fluorinated polymer having a sulfonic acid group (hereinafter, referred to as S polymer), and having inorganic particles attached to the surface. After removing the inorganic particles on the surface by swelling the film with a solvent, the film was brought into contact with a solvent that is a good solvent for the S polymer and a poor solvent for the C polymer, thereby dissolving the solid consisting mainly of the C polymer and the S polymer. A method for recovering a fluoropolymer, comprising obtaining a solution and recovering the solution by solid-liquid separation.
の有機溶媒と水との混合溶媒である請求項１記載の含フ
ッ素ポリマーの回収方法。2. The method according to claim 1, wherein the solvent for swelling the ion exchange membrane is a mixed solvent of a water-soluble organic solvent and water.
ーの貧溶媒である溶媒は、該溶媒に対するＳポリマーの
溶解度が、該溶媒に対するＣポリマーの溶解度の１０倍
以上である請求項１または２記載の含フッ素ポリマーの
回収方法。3. The solvent that is a good solvent for the S polymer and a poor solvent for the C polymer has a solubility of the S polymer in the solvent of at least 10 times the solubility of the C polymer in the solvent. 3. The method for recovering a fluoropolymer according to 2.
Ｓポリマーの良溶媒であり、かつＣポリマーの貧溶媒で
ある溶媒に接触させる前に、酸で処理することによりＣ
ポリマーおよびＳポリマーを塩型から酸型に変換する請
求項１〜３いずれか記載の含フッ素ポリマーの回収方
法。4. The ion-exchange membrane from which inorganic particles have been removed,
Before contact with a solvent that is a good solvent for the S-polymer and a poor solvent for the C-polymer,
The method for recovering a fluoropolymer according to any one of claims 1 to 3, wherein the polymer and the S polymer are converted from a salt form to an acid form.
と、カルボン酸基を有するパーフルオロビニルエーテル
とを重合させてなる共重合体であって、イオン交換容量
が０．８〜１．９ミリ当量／ｇ乾燥樹脂である請求項１
〜４いずれか記載の含フッ素ポリマーの回収方法。5. The C polymer is a copolymer obtained by polymerizing tetrafluoroethylene and perfluorovinyl ether having a carboxylic acid group, and has an ion exchange capacity of 0.8 to 1.9 meq / g. 2. A dry resin.
5. The method for recovering a fluorine-containing polymer according to any one of items 4 to 4.
と、スルホン酸基を有するパーフルオロビニルエーテル
とを重合させてなる共重合体であって、イオン交換容量
が０．８〜１．３ミリ当量／ｇ乾燥樹脂である請求項１
〜５いずれか記載の含フッ素ポリマーの回収方法。6. The S-polymer is a copolymer obtained by polymerizing tetrafluoroethylene and a perfluorovinyl ether having a sulfonic acid group, and has an ion exchange capacity of 0.8 to 1.3 meq / g. 2. A dry resin.
6. The method for recovering a fluoropolymer according to any one of claims 5 to 5.
Priority Applications (1)
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|---|---|---|---|
| JP2002030881A JP4042421B2 (en) | 2001-03-07 | 2002-02-07 | Method for recovering fluoropolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-63503 | 2001-03-07 | ||
| JP2001063503 | 2001-03-07 | ||
| JP2002030881A JP4042421B2 (en) | 2001-03-07 | 2002-02-07 | Method for recovering fluoropolymer |
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| Publication Number | Publication Date |
|---|---|
| JP2002332376A true JP2002332376A (en) | 2002-11-22 |
| JP4042421B2 JP4042421B2 (en) | 2008-02-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2002030881A Expired - Fee Related JP4042421B2 (en) | 2001-03-07 | 2002-02-07 | Method for recovering fluoropolymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007119739A1 (en) * | 2006-04-12 | 2007-10-25 | Daikin Industries, Ltd. | Method for producing reclaimed material |
| CN116478448A (en) * | 2023-06-20 | 2023-07-25 | 国家电投集团氢能科技发展有限公司 | Method for recycling perfluorinated sulfonic acid resin by using water electrolysis membrane |
-
2002
- 2002-02-07 JP JP2002030881A patent/JP4042421B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007119739A1 (en) * | 2006-04-12 | 2007-10-25 | Daikin Industries, Ltd. | Method for producing reclaimed material |
| CN116478448A (en) * | 2023-06-20 | 2023-07-25 | 国家电投集团氢能科技发展有限公司 | Method for recycling perfluorinated sulfonic acid resin by using water electrolysis membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4042421B2 (en) | 2008-02-06 |
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