JPH06199958A - Production of perfluorocarbon polymer having sulfonic acid-type functional group - Google Patents
Production of perfluorocarbon polymer having sulfonic acid-type functional groupInfo
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- JPH06199958A JPH06199958A JP36051192A JP36051192A JPH06199958A JP H06199958 A JPH06199958 A JP H06199958A JP 36051192 A JP36051192 A JP 36051192A JP 36051192 A JP36051192 A JP 36051192A JP H06199958 A JPH06199958 A JP H06199958A
- Authority
- JP
- Japan
- Prior art keywords
- sulfonic acid
- functional group
- hydrofluorocarbon
- type functional
- perfluorocarbon
- Prior art date
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、スルホン酸型官能基を
有するパーフルオロカーボン重合体の製造方法に関する
ものである。TECHNICAL FIELD The present invention relates to a method for producing a perfluorocarbon polymer having a sulfonic acid type functional group.
【０００２】[0002]
【従来の技術】従来、ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ
3 ）ＯＣＦ2 ＣＦ2 ＳＯ2 Ｆの如きスルホン酸型官能基
を有するモノマーとＣＦ2 ＝ＣＦ2 の如きフルオロオレ
フィンとの共重合により、高イオン交換容量のパーフル
オロカーボン重合体を得る方法として、塊状重合あるい
はフッ素系溶剤を媒体とする溶液重合が採用されてい
る。 2. Description of the Related Art Conventionally, CF 2 = CFOCF 2 CF (CF
3) the copolymerization of OCF 2 CF 2 SO-mentioned fluoroolefin monomer and CF 2 = CF 2 with 2 F such sulfonic acid functional groups, as a method of obtaining a perfluorocarbon polymer having a high ion exchange capacity, bulk Polymerization or solution polymerization using a fluorinated solvent as a medium is adopted.
【０００３】特に製造時の除熱、撹拌混合の容易さなど
の点より溶液重合が好ましく採用されており、媒体とし
てトリクロロトリフロロエタン（特公昭４６−２３２４
５）やパーフルオロジメチルシクロブタン（ＵＳ ３，
２８２，８７５）を使用した実施例が記載されている。
また、ＣＦ2 ＝ＣＦＯ（ＣＦ2 ）3 ＳＣ2 Ｈ5 とＣＦ2
＝ＣＦ2 の共重合にもトリクロロトリフロロエタンなど
のパーフルオロ炭化水素媒体が使用できることが特開昭
５５−１６０００７などに記載されている。In particular, solution polymerization is preferably adopted in terms of heat removal during production, ease of stirring and mixing, and the like, and trichlorotrifluoroethane (Japanese Patent Publication No. 46-2324) is used as a medium.
5) and perfluorodimethylcyclobutane (US 3,
282,875) is used.
In addition, CF 2 = CFO (CF 2 ) 3 SC 2 H 5 and CF 2
It is described in JP-A-55-160007 that a perfluorohydrocarbon medium such as trichlorotrifluoroethane can be used for the copolymerization of ═CF 2 .
【０００４】しかしながら、従来の溶液重合で採用され
ていた、入手が容易で安価なトリクロロトリフルオロエ
タンの如き特定のフッ素溶剤は大気中のオゾンを破壊す
る恐れから、その使用が制限されることとなっており、
それに代わる重合溶剤の開発が要請されていた。一方、
パーフルオロ炭化水素媒体は、入手が容易でなかった
り、高価なものが多く、また生成ポリマーの分子量の調
節や炭化水素系の開始剤の溶解性が十分でないなど代替
え溶媒として十分なものといえなかった。However, the use of a specific fluorine solvent such as trichlorotrifluoroethane, which has been adopted in the conventional solution polymerization and which is easily available and inexpensive, may limit the use of ozone because it may destroy ozone in the atmosphere. Has become
The development of an alternative polymerization solvent has been demanded. on the other hand,
Perfluorohydrocarbon media are not readily available, are often expensive, and cannot be said to be sufficient as alternative solvents because the molecular weight of the produced polymer is controlled and the solubility of hydrocarbon-based initiators is insufficient. It was
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記問題を
解決すべくなされたものであって、スルホン酸型官能基
を含有するパーフルオロカーボンモノマーとパーフルオ
ロオレフィンを共重合せしめる方法において、水素とフ
ッ素を含有する炭化水素である、ハイドロフルオロカー
ボンを媒体とすることを特徴とするパーフルオロカーボ
ン重合体の製造方法を提供するものである。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and in the method of copolymerizing a perfluorocarbon monomer containing a sulfonic acid type functional group and a perfluoroolefin, The present invention provides a method for producing a perfluorocarbon polymer, characterized in that a medium is hydrofluorocarbon, which is a hydrocarbon containing fluorine.
【０００６】[0006]
【課題を解決するための手段】本発明の重合媒体として
用いられるハイドロフルオロカーボンとしては、好まし
くは一般式Ｃn Ｈm Ｆ2n+2-m（但し、ｎは３〜１６の整
数であり、ｍ／２ｎ＋２−ｍ＝６０／４０〜５／９５で
ある）が用いられ。炭素数がこれより少ないと沸点が低
すぎ、これより多いと高すぎる。より好ましくは、ｎは
４〜１０の範囲であり、線状、分岐状、環状のいずれで
あってもよい。またハイドロフルオロカーボン中の炭素
原子へ結合する水素原子数が多すぎると、生成ポリマー
の分子量が小さくなり、一方少なすぎると分子量が大き
くなりすぎたり、開始剤の溶解性が不十分となる。好ま
しくはＨ／Ｆ（モル比）が６０／４０〜５／９５の範囲
であり、より好ましくは５０／５０〜１０／９０であ
る。The hydrofluorocarbon used as the polymerization medium of the present invention is preferably represented by the general formula C n H m F 2n + 2-m (where n is an integer of 3 to 16 and m / 2n + 2-m = 60/40 to 5/95) is used. When the carbon number is less than this, the boiling point is too low, and when it is more than this, the boiling point is too high. More preferably, n is in the range of 4 to 10, and may be linear, branched or cyclic. If the number of hydrogen atoms bonded to carbon atoms in the hydrofluorocarbon is too large, the molecular weight of the produced polymer will be small, while if it is too small, the molecular weight will be too large and the solubility of the initiator will be insufficient. The H / F (molar ratio) is preferably in the range of 60/40 to 5/95, and more preferably 50/50 to 10/90.
【０００７】このようなハイドロフルオロカーボンの具
体例を記載すれば、Ｃ2 Ｆ5 Ｃ2 Ｈ5 、ＣＨＦ2 ＣＦ2
ＣＦ2 ＣＨＦ2 、ＣＨ3 ＣＦ2 ＣＦＨＣＦ3 、（ＣＦ
3 ）2ＣＦＣ2 Ｈ5 、ＣＨ3 ＣＨＦＣ2 Ｆ5 Ｃ2 Ｈ5 、
ＣＨ3 ＣＦ2 ＣＦ2 ＣＦ2 ＣＦ2 Ｈ、Ｃ4 Ｆ9 Ｃ2 Ｈ
5 、Ｃ2 Ｆ5 Ｃ2 Ｈ4 Ｃ2 Ｆ5 、（ＣＦ3 ）2 ＣＦＣＨ
ＦＣＨＦＣＦ3 、ＣＨ3 ＣＦ2 ＣＦ2 ＣＦ2 ＣＦ2 ＣＦ
2 ＣＦ2 Ｈ、Ｃ6 Ｆ13Ｃ2Ｈ5 、Ｃ2 Ｈ5 Ｃ2 Ｆ4 Ｃ2
Ｈ5 、Ｃ8 Ｆ17Ｃ2 Ｈ5 などである。Specific examples of such a hydrofluorocarbon will be described below. C 2 F 5 C 2 H 5 and CHF 2 CF 2
CF 2 CHF 2 , CH 3 CF 2 CFHCF 3 , (CF
3 ) 2 CFC 2 H 5 , CH 3 CHFC 2 F 5 C 2 H 5 ,
CH 3 CF 2 CF 2 CF 2 CF 2 H, C 4 F 9 C 2 H
5 , C 2 F 5 C 2 H 4 C 2 F 5 , (CF 3 ) 2 CFCH
FCHFCF 3 , CH 3 CF 2 CF 2 CF 2 CF 2 CF
2 CF 2 H, C 6 F 13 C 2 H 5 , C 2 H 5 C 2 F 4 C 2
, Etc. H 5, C 8 F 17 C 2 H 5.
【０００８】本発明において、採用されるスルホン酸型
官能基含有パーフルオロカーボンモノマーとしては、従
来より公知乃至周知のものなどが広範囲にわたって例示
され得る。In the present invention, as the sulfonic acid type functional group-containing perfluorocarbon monomer to be employed, those known or well known can be exemplified in a wide range.
【０００９】好適なものとしては、一般式、ＣＦ2 ＝Ｃ
Ｆ（ＯＣＦ2 ＣＦＸ）p −（Ｏ）q−（ＣＦ2 ）r −
（ＣＦ2 ＣＦＸ′）s −Ａ （式中、ｐは０〜３、ｓは０〜３、ｒは０〜１２、ｑは
０又は１であり、Ｘは−Ｆ又は−ＣＦ3 であり、Ｘ′は
−Ｆ又は−ＣＦ3 であり、Ａはスルホン酸型官能基であ
る）で表わされるフルオロビニル化合物が例示される。
通常は入手容易性などの点から、Ｘ及びＸ′は−ＣＦ
3 、ｐは０又は１、ｓは０、ｒは０〜８、ｑは０又は１
であり、またＡは共重合反応性などから−ＳＯ2 Ｆが好
ましい。Preferred is the general formula CF 2 ═C
F (OCF 2 CFX) p - (O) q - (CF 2) r -
(CF 2 CFX ') s -A ( wherein, p is 0 to 3, s is 0 to 3, r is 0 to 12, q is 0 or 1, X is -F or -CF 3, X ′ is —F or —CF 3 , and A is a sulfonic acid type functional group).
Usually, X and X ′ are —CF in view of easy availability.
3 , p is 0 or 1, s is 0, r is 0-8, q is 0 or 1.
And A is preferably —SO 2 F from the viewpoint of copolymerization reactivity.
【００１０】かかるフルオロビニル化合物の好ましい代
表例としては、 ＣＦ2 ＝ＣＦＯ（ＣＦ2 )1-8ＳＯ2 Ｆ, ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3 ）Ｏ（ＣＦ2 )1-8Ｓ
Ｏ2 Ｆ, ＣＦ2 ＝ＣＦ（ＣＦ2 )0-8ＳＯ2 Ｆ, ＣＦ2 ＝ＣＦ（ＯＣＦ2 ＣＦ（ＣＦ3 ))1-5 ＯＣＦ2 Ｃ
Ｆ2 ＳＯ2 Ｆ 等があげられる。A preferred representative example of such a fluorovinyl compound is CF 2 ═CFO (CF 2 ) 1-8 SO 2 F, CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 1-8 S
O 2 F, CF 2 = CF (CF 2 ) 0-8 SO 2 F, CF 2 = CF (OCF 2 CF (CF 3 )) 1-5 OCF 2 C
Examples include F 2 SO 2 F.
【００１１】本発明においては、テトラフルオロエチレ
ンと上述の如きスルホン酸型官能基含有パーフルオロカ
ーボンモノマーとがハイドロフルオロカーボン中共重合
せしめられるが、スルホン酸型官能基含有パーフルオロ
カーボンモノマーを二種以上で使用できるだけでなく、
これらモノマーの他に、他の成分、例えばカルボン酸型
官能基含有パーフルオロカーボンモノマー、ＣＦ2 ＝Ｃ
ＦＯＲf （Ｒf は炭素数１〜１０のパーフルオロアルキ
ル基を示す）、あるいはＣＦ2 ＝ＣＦ−ＣＦ＝ＣＦ2 、
ＣＦ2 ＝ＣＦＯ（ＣＦ2 ）1-4 ＯＣＦ＝ＣＦ2 の如きジ
ビニルモノマーなどの一種又は二種以上を併用すること
もできる。In the present invention, tetrafluoroethylene and a sulfonic acid type functional group-containing perfluorocarbon monomer as described above can be copolymerized in a hydrofluorocarbon. However, two or more sulfonic acid type functional group-containing perfluorocarbon monomers can be used. Not
In addition to these monomers, other components such as carboxylic acid type functional group-containing perfluorocarbon monomers, CF 2 ═C
FOR f (R f represents a perfluoroalkyl group having 1 to 10 carbon atoms) or CF 2 ═CF—CF═CF 2 ,
CF 2 = CFO (CF 2) 1-4 can be used in combination one or two or more of such such divinyl monomers OCF = CF 2.
【００１２】しかして、本発明においては、ハイドロフ
ルオロカーボン中の共重合によりスルホン酸型官能基含
有パーフルオロカーボンモノマーが高割合で共重合した
パーフルオロカーボン重合体を目的としているので、通
常は該スルホン酸型官能基含有パーフルオロカーボンモ
ノマーの共重合割合が２０重量％以上であるパーフルオ
ロカーボン重合体を生成せしめるべく、上記各種モノマ
ーの使用割合を選定するのが望ましい。特に、スルホン
酸型官能基含有パーフルオロカーボンモノマーの共重合
割合が２５〜６０重量％程度のパーフルオロカーボン重
合体を生成せしめるべく、選定されるのが好ましい。In the present invention, however, since a perfluorocarbon polymer in which a sulfonic acid type functional group-containing perfluorocarbon monomer is copolymerized in a high proportion by copolymerization in a hydrofluorocarbon is used, the sulfonic acid type is usually used. In order to produce a perfluorocarbon polymer in which the copolymerization ratio of the functional group-containing perfluorocarbon monomer is 20% by weight or more, it is desirable to select the use ratios of the above various monomers. In particular, it is preferable to select it so as to produce a perfluorocarbon polymer in which the copolymerization ratio of the sulfonic acid type functional group-containing perfluorocarbon monomer is about 25 to 60% by weight.
【００１３】本発明により得られるスルホン酸型パーフ
ルオロカーボン重合体をイオン交換膜として使用する場
合には、そのイオン交換容量は、０．５〜２．０ミリ当
量グラム乾燥樹脂という広い範囲から選択されるが、以
下に述べる如き条件を採用することにより、イオン交換
容量を大きくしても、生成共重合体の分子量を高くで
き、従って共重合体の機械的性質や耐久性は低下するこ
とがない。イオン交換容量は、上記の範囲でも、共重合
体の種類に応じて異なるが、好ましくは０．６ミリ当量
／グラム乾燥樹脂以上、特に０．７ミリ当量／グラム乾
燥樹脂以上の場合が、イオン交換膜としての機械的性質
及び電気化学的性能上好ましい。When the sulfonic acid type perfluorocarbon polymer obtained by the present invention is used as an ion exchange membrane, its ion exchange capacity is selected from a wide range of 0.5 to 2.0 meq. Gram dry resin. However, by adopting the conditions described below, the molecular weight of the produced copolymer can be increased even if the ion exchange capacity is increased, and therefore the mechanical properties and durability of the copolymer are not deteriorated. . Although the ion exchange capacity varies depending on the type of the copolymer even in the above range, the ion exchange capacity is preferably 0.6 meq / g dry resin or more, particularly 0.7 meq / g dry resin or more. It is preferable in terms of mechanical properties and electrochemical performance as an exchange membrane.
【００１４】また、本発明で得られるスルホン酸型パー
フルオロカーボン重合体の分子量は、イオン交換膜とし
ての機械的性能及び製膜性と関係するので重要であり、
ＴQの値で表示すると、１５０℃以上、 好ましくは１７
０〜３４０℃、特に１８０〜２８０℃程度とするのが好
適である。The molecular weight of the sulfonic acid type perfluorocarbon polymer obtained in the present invention is important because it is related to the mechanical performance and film-forming property as an ion exchange membrane,
When expressed as a value of T Q , it is 150 ° C or higher, preferably 17
The temperature is preferably 0 to 340 ° C., particularly 180 to 280 ° C.
【００１５】本明細書中において「ＴQ 」なる言葉は、
次のように定義されるものである。即ち、共重合体の分
子量に関係する容量流速１００ｍｍ3 ／秒を示す温度が
ＴQと定義される。ここにおいて容量流速は、共重合体
を３０ｋｇ／ｃｍ2 加圧のもとに、一定温度に保持した
径１ｍｍ、長さ２ｍｍのオリフィスから溶融流出せし
め、流出する共重合体量をｍｍ3 ／秒の単位で示したも
のである。In this specification, the term "T Q " means
It is defined as follows. That is, the temperature at which a volumetric flow rate of 100 mm 3 / sec related to the molecular weight of the copolymer is defined as T Q. Here, the volumetric flow rate is such that the copolymer is melted and flown out from an orifice having a diameter of 1 mm and a length of 2 mm, which is kept at a constant temperature, under a pressure of 30 kg / cm 2 , and the amount of the copolymer flowing out is mm 3 / sec. It is shown in units of.
【００１６】なお、「イオン交換容量」は、次のように
して求めた。即ち、Ｈ型の陽イオン交換樹脂膜を、１Ｎ
のＨＣｌ中で６０℃、５時間放置し、完全にＨ型に転換
し、ＨＣｌが残存しないように水で充分洗浄した。その
後、このＨ型の膜０．５ｇを、０．１ＮのＮａＯＨ ２
５ｍｌに水を２５ｍｌ加えてなる溶液中に、室温で２日
間静置した。次いで膜をとり出して、溶液中のＮａＯＨ
の量を０．１ＮのＨＣｌで逆滴定することにより求める
ものである。The "ion exchange capacity" was determined as follows. That is, the H-type cation exchange resin membrane is
It was left to stand in HCl of 60 ° C. for 5 hours, completely converted to H-form, and washed sufficiently with water so that HCl did not remain. Then, 0.5 g of this H-type film was added to 0.1 N NaOH 2
The mixture was allowed to stand at room temperature for 2 days in a solution prepared by adding 25 ml of water to 5 ml. The membrane is then removed and the NaOH in solution is removed.
Is determined by back titration with 0.1 N HCl.
【００１７】本発明においては、スルホン酸型モノマー
など官能性単量体とパーフルオロオレフィンとの共重合
反応を、ハイドロフルオロカーボンの使用量をハイドロ
フルオロカーボン／官能性単量体を、重量比で２０／１
以下にし、好ましくは１０／１以下に制御して実施する
ことが好適である。ハイドロフルオロカーボン媒体の使
用量が多すぎる場合には、反応装置の大型化あるいは共
重合体分離回収など作業操作面の不利があげられる。In the present invention, the copolymerization reaction of a functional monomer such as a sulfonic acid type monomer with a perfluoroolefin is carried out, and the amount of hydrofluorocarbon used is 20% by weight of hydrofluorocarbon / functional monomer. 1
It is preferable to carry out the treatment at a controlled temperature of 10/1 or less. If the amount of the hydrofluorocarbon medium used is too large, there are disadvantages in terms of work operation such as enlargement of the reactor or separation and recovery of the copolymer.
【００１８】次に、本発明においては、１ｋｇ／ｃｍ2
以上の共重合反応圧力を採用することが好適である。共
重合反応圧力が低すぎる場合には、共重合反応速度を実
用上満足し得る高さに維持することが困難であり、高分
子量の共重合体の形成に難点が認められる。また、共重
合反応圧力が低すぎると、生成共重合体のイオン交換容
量が高くなり、含水量増大などによる機械的強度、イオ
ン交換性能の低下傾向が増大することになる。Next, in the present invention, 1 kg / cm 2
It is preferable to adopt the above copolymerization reaction pressure. When the copolymerization reaction pressure is too low, it is difficult to maintain the copolymerization reaction rate at a level that is practically satisfactory, and it is difficult to form a high molecular weight copolymer. On the other hand, if the copolymerization reaction pressure is too low, the ion exchange capacity of the produced copolymer becomes high, and the mechanical strength and the ion exchange performance tend to decrease due to an increase in the water content.
【００１９】なお、共重合反応圧力は、工業的実施にお
ける反応装置上又は作業操作上などを考慮して、５０ｋ
ｇ／ｃｍ2 以下から選定されるのが望ましい。かかる範
囲よりも高い共重合反応圧力の採用は可能であるが、本
発明の目的を比例的に向上せしめ得るものではない。従
って、本発明においては、共重合反応圧力を２〜５０ｋ
ｇ／ｃｍ2 、好ましくは２〜３０ｋｇ／ｃｍ2 の範囲か
ら選定するのが最適である。The copolymerization reaction pressure is set to 50 k in consideration of the reaction apparatus or the work operation in industrial practice.
It is desirable to be selected from g / cm 2 or less. It is possible to employ a copolymerization reaction pressure higher than this range, but it is not possible to proportionally improve the object of the present invention. Therefore, in the present invention, the copolymerization reaction pressure is 2 to 50 k.
It is optimum to select from the range of g / cm 2 , preferably 2 to 30 kg / cm 2 .
【００２０】本発明の共重合反応に際しては、前記反応
条件の他の条件や操作は、特に限定されることなく広い
範囲にわたって採用され得る。例えば、共重合反応温度
は、重量開始源の種類や反応モル比などにより最適値が
選定され得るが、通常は余りに高温度や低温度は工業的
実施に対して不利となるので、２０〜９０℃、好ましく
は３０〜８０℃程度から選定される。In the copolymerization reaction of the present invention, other conditions and operations other than the above reaction conditions are not particularly limited and can be adopted over a wide range. For example, the copolymerization reaction temperature may be selected as an optimum value depending on the type of the weight initiation source, the reaction molar ratio, etc. However, usually too high temperature or too low temperature is disadvantageous to industrial practice, and therefore 20 to 90. C., preferably about 30 to 80.degree.
【００２１】しかして、本発明において重合開始源とし
ては、前記の好適な反応温度において高い活性を示すも
のを選定するのが望ましい。例えば、室温以下でも高活
性の電離性放射線を採用することもできるが、通常はア
ゾ化合物やパーオキシ化合物を採用する方が工業的実施
に対して有利である。Therefore, in the present invention, it is desirable to select, as the polymerization initiation source, one which exhibits high activity at the above-mentioned suitable reaction temperature. For example, ionizing radiation having high activity even at room temperature or lower can be adopted, but it is usually more advantageous for industrial practice to use an azo compound or a peroxy compound.
【００２２】本発明で好適に採用される重合開始源は前
記共重合反応条件下に２０〜９０℃程度で高活性を示す
ジコハク酸パーオキサイド、ベンゾイルパーオキサイ
ド、ラウロイルパーオキサイド、ジペンタフルオロプロ
ピオニルパーオキサイド等のジアシルパーオキサイド、
２，２′−アゾビス（２−アミジノプロパン）塩酸塩、
４，４′−アゾビス（４−シアノワレリアン酸）、アゾ
ビスイソブチロニトリル等のアゾ化合物、ｔ−ブチルパ
ーオキシイソブチレート、ｔ−ブチルパーオキシピバレ
ート等のパーオキシエステル類、ジイソプロピルパーオ
キシジカーボネート、ジ−２−エチルヘキシルパーオキ
シジカーボネート等のパーオキシジカーボネート、ジイ
ソプロピルベンゼンハイドロパーオキサイド等のハイド
ロパーオキサイド類である。The polymerization initiation source preferably used in the present invention is disuccinic acid peroxide, benzoyl peroxide, lauroyl peroxide, dipentafluoropropionyl peroxide, which exhibits high activity at about 20 to 90 ° C. under the copolymerization reaction conditions. Diacyl peroxide such as oxide,
2,2'-azobis (2-amidinopropane) hydrochloride,
Azo compounds such as 4,4′-azobis (4-cyanovaleric acid) and azobisisobutyronitrile, peroxyesters such as t-butylperoxyisobutyrate and t-butylperoxypivalate, diisopropyl Peroxydicarbonates such as peroxydicarbonate and di-2-ethylhexyl peroxydicarbonate, and hydroperoxides such as diisopropylbenzene hydroperoxide.
【００２３】本発明においては、重合開始源濃度は、全
モノマーに対して0.0001〜３重量％、好ましくは0.0001
〜２重量％程度である。開始源濃度を下げることによっ
て、生成共重合体の分子量を高めることが可能であり、
高イオン交換容量を保持することが可能である。開始源
濃度を余りに高くすると、分子量の低下傾向が増し、高
イオン交換容量で高分子量の共重合体の生成に対して不
利となる。その他通常の溶液重合において用いられる分
子量調整剤等を添加することもできる。また、本発明に
おける共重合反応を阻害しないもので、連鎖移動の少な
いものであれば、不活性有機溶媒を添加することもでき
る。In the present invention, the concentration of the polymerization initiation source is 0.0001 to 3% by weight, preferably 0.0001, based on all the monomers.
It is about 2% by weight. By lowering the starting source concentration, it is possible to increase the molecular weight of the resulting copolymer,
It is possible to maintain a high ion exchange capacity. If the starting source concentration is too high, the tendency of lowering the molecular weight increases, which is disadvantageous to the formation of a high ion exchange capacity, high molecular weight copolymer. In addition, a molecular weight modifier or the like used in ordinary solution polymerization may be added. Further, an inert organic solvent may be added as long as it does not inhibit the copolymerization reaction in the present invention and has little chain transfer.
【００２４】しかして、本発明においては、生成共重合
体濃度を４０重量％以下、好ましくは３０重量％以下に
制御して実施するのが好適である。余りに高濃度にする
と、共重合体組成の不均一性の増大、重合トルクの増大
などによる撹拌の停止などの難点が認められる。Therefore, in the present invention, it is preferable to control the concentration of the produced copolymer to 40% by weight or less, preferably 30% by weight or less. If the concentration is too high, problems such as an increase in the non-uniformity of the copolymer composition and an agitation due to an increase in the polymerization torque are recognized.
【００２５】本発明で製造されるスルホン酸型パーフル
オロカーボン重量体は、種々の分野で使用されるが、例
えばイオン交換膜として好適に使用される。イオン交換
膜に使用する場合、スルホン酸型パーフルオロカーボン
重量体は、適宜手段にて製膜され得る。例えば、必要に
より官能基を加水分解でスルホン酸基に転換するが、か
かる加水分解処理は製膜前でも製膜後でも可能である。
通常は製膜後に加水分解処理する方が望ましい。製膜手
段には種々のものが採用可能であり、例えば加熱熔融成
形、ラテックス成形、適当な溶液に溶解させての注型成
形など公知乃至周知の方法を適宜採用し得る。更に、異
なるイオン交換容量を有する膜或いはカルボン酸基等の
異なる官能基を有する膜と２層以上に積層することも可
能である。また、クロス、繊維、不織布等による補強を
加えることもできる。The sulfonic acid type perfluorocarbon weight product produced by the present invention is used in various fields, and is preferably used as, for example, an ion exchange membrane. When used for an ion exchange membrane, the sulfonic acid type perfluorocarbon weight body can be formed into a membrane by an appropriate means. For example, if necessary, the functional group is hydrolyzed to be converted into a sulfonic acid group, and such a hydrolysis treatment can be performed before or after film formation.
Usually, it is desirable to carry out hydrolysis treatment after film formation. Various kinds of film forming means can be adopted, and for example, known or well-known methods such as hot melt molding, latex molding, and cast molding by dissolving in a suitable solution can be appropriately adopted. Furthermore, it is also possible to laminate two or more layers with a film having a different ion exchange capacity or a film having a different functional group such as a carboxylic acid group. Further, reinforcement with cloth, fibers, non-woven fabric or the like can be added.
【００２６】本発明で製造されるスルホン酸型パーフル
オロカーボン重合体からのイオン交換膜は、種々の優れ
た性能を有するために、各種分野、目的、用途などに広
範囲に採用され得る。例えば、拡散透析、オゾン発生電
解、電解還元、燃料電池の隔膜、高分子触媒などとし
て、特に耐触性が要求される分野で好適に使用される。
なかでも、アルカリ電解用の陽イオン交換膜として使う
場合には、カルボン酸型膜との積層膜などにおいて高い
性能を発揮し得るものである。The ion exchange membrane made from the sulfonic acid type perfluorocarbon polymer produced in the present invention has various excellent properties and thus can be widely adopted in various fields, purposes and applications. For example, it is suitably used as a diffusion dialysis, an ozone generating electrolysis, an electrolytic reduction, a membrane of a fuel cell, a polymer catalyst, etc., particularly in a field requiring touch resistance.
In particular, when it is used as a cation exchange membrane for alkaline electrolysis, it can exhibit high performance in a laminated membrane with a carboxylic acid type membrane.
【００２７】例えば、上記のような陽イオン交換膜に
て、陽極と陰極とを区画して陽極室と陰極室とを構成
し、陽極室に塩化アルカリ水溶液を供給して電解し、陰
極室から水酸化アルカリを得る所謂二室型槽の場合で
も、２規定以上の濃度の塩化ナトリム水溶液を原料にし
て５〜５０Ａ／ｄｍ2 の電流密度で電解することによ
り、３０％以上の高濃度の水酸化ナトリウムが高い電流
効率と低い槽電圧で長期にわたって安定して製造でき
る。For example, in the cation exchange membrane as described above, the anode and the cathode are divided to form an anode chamber and a cathode chamber, and an alkaline chloride aqueous solution is supplied to the anode chamber to electrolyze. Even in the case of a so-called two-chamber type tank for obtaining alkali hydroxide, a high concentration water of 30% or more is obtained by electrolyzing a sodium chloride aqueous solution having a concentration of 2 N or more as a raw material at a current density of 5 to 50 A / dm 2. Sodium oxide can be stably manufactured over a long period of time with high current efficiency and low cell voltage.
【００２８】次に、本発明の実施例について、更に具体
的に説明するが、かかる説明によって本発明が限定され
るものでないことは勿論である。Next, the embodiments of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations.
【００２９】[0029]
［実施例１］Ｃ8 Ｆ17Ｃ2 Ｈ5 ６８ｇ、アゾビスイソブ
チロニトリル ０．０８ｇ、及びＣＦ2 ＝ＣＦＯＣＦ2
ＣＦ（ＣＦ3 ）ＯＣＦ2 ＣＦ2 ＳＯ2 Ｆ ９２．２ｇを
内容積０．２リットルのステンレス製オートクレーブに
仕込み、液体チッ素で十分脱気した後、温度を７０℃と
し、テトラフルオロエチレンを導入し、圧力を一定に保
持した。８時間後に未反応のテトラフルオロエチレンを
パージして重合を終了させ、得られたポリマー溶液をメ
タノールで凝集し、洗浄、乾燥を行なって１８ｇの共重
合体を得た。Example 1 68 g of C 8 F 17 C 2 H 5 , 0.08 g of azobisisobutyronitrile, and CF 2 ═CFOCF 2
92.2 g of CF (CF 3 ) OCF 2 CF 2 SO 2 F was charged into a stainless steel autoclave with an internal volume of 0.2 liter, sufficiently degassed with liquid nitrogen, and the temperature was raised to 70 ° C., and tetrafluoroethylene was introduced. The pressure was kept constant. After 8 hours, unreacted tetrafluoroethylene was purged to terminate the polymerization, and the obtained polymer solution was coagulated with methanol, washed and dried to obtain 18 g of a copolymer.
【００３０】該共重合体のイオン交換容量は１．１ミリ
当量／グラム乾燥樹脂であった。該共重合体を２５０℃
でプレス製膜すると強靭なフィルムが得られ、２５％Ｎ
ａＯＨ水溶液で加水分解するとスルホン酸型イオン交換
膜が得られた。The ion exchange capacity of the copolymer was 1.1 meq / g dry resin. 250 ° C. of the copolymer
A tough film is obtained by press forming with 25% N
When hydrolyzed with an aOH aqueous solution, a sulfonic acid type ion exchange membrane was obtained.
【００３１】［実施例２］Ｃ8 Ｆ17Ｃ2 Ｈ5 に代えて、
Ｃ4 Ｆ7 Ｃ2 Ｈ5 を用いる以外は、実施例１同様にして
重合を行い、イオン交換容量１．０ミリ当量／グラム乾
燥樹脂の共重合体を得た。[Example 2] Instead of C 8 F 17 C 2 H 5 ,
Polymerization was carried out in the same manner as in Example 1 except that C 4 F 7 C 2 H 5 was used to obtain a copolymer of ion exchange capacity of 1.0 meq / g dry resin.
【００３２】[0032]
【発明の効果】スルホン酸型官能基を有するパーフルオ
ロカーボン共重合体を容易に、かつ特定フロンを使用せ
ずオゾン破壊の恐れの少ない媒体中で製造できる。EFFECTS OF THE INVENTION A perfluorocarbon copolymer having a sulfonic acid type functional group can be easily produced in a medium in which ozone depletion is less likely to occur without using a specific chlorofluorocarbon.
Claims (5)
ボンモノマーとパーフルオロオレフィンを共重合せしめ
る方法において、ハイドロフルオロカーボンを媒体とす
ることを特徴とするパーフルオロカーボン重合体の製造
方法。1. A method for producing a perfluorocarbon polymer, characterized in that a hydrofluorocarbon is used as a medium in a method of copolymerizing a perfluorocarbon monomer having a sulfonic acid type functional group and a perfluoroolefin.
Ｈm Ｆ2n+2-m（但し、ｎは３〜１６の整数、ｍ／（２ｎ
＋２−ｍ）は６０／４０〜５／９５である。）で示され
る請求項１の製造方法。2. Hydrofluorocarbon is represented by the general formula, C n
H m F 2n + 2-m (where n is an integer of 3 to 16, m / (2n
+ 2-m) is 60/40 to 5/95. ] The manufacturing method of Claim 1 shown by these.
2 Ｆ5 Ｃ2 Ｈ5 、Ｒf Ｃ2 Ｈ5 （但し、Ｒf はＣj Ｆ
2j+1 であり、ｊは２〜８の整数である。）で示される
請求項１の製造方法。3. Hydrofluorocarbon is represented by the general formula: C
2 F 5 C 2 H 5 , R f C 2 H 5 (where R f is C j F
2j + 1 , and j is an integer of 2-8. ] The manufacturing method of Claim 1 shown by these.
2 Ｈ5 、Ｃ4 Ｆ9 Ｃ2 Ｈ5 、Ｃ6 Ｆ13Ｃ2 Ｈ5 又はＣ8
Ｆ17Ｃ2 Ｈ5 である請求項１の製造方法。4. The hydrofluorocarbon is C 2 F 5 C.
2 H 5 , C 4 F 9 C 2 H 5 , C 6 F 13 C 2 H 5 or C 8
The method according to claim 1, which is F 17 C 2 H 5 .
ボンモノマーが、ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3 ）
ＯＣＦ2 ＣＦ2 ＳＯ2 Ｆであって、これと共重合させる
パーフルオロオレフィンがＣＦ2 ＝ＣＦ2 であり、前者
の共重合割合が２０重量％以上である請求項１，２，３
又は４の製造方法。5. A sulfonic acid type functional group-containing perfluorocarbon monomer is CF 2 ═CFOCF 2 CF (CF 3 ).
4. OCF 2 CF 2 SO 2 F, the perfluoroolefin to be copolymerized therewith is CF 2 = CF 2 , and the former copolymerization ratio is 20% by weight or more.
Or the manufacturing method of 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36051192A JP3356474B2 (en) | 1992-12-28 | 1992-12-28 | Method for producing perfluorocarbon polymer having sulfonic acid type functional group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36051192A JP3356474B2 (en) | 1992-12-28 | 1992-12-28 | Method for producing perfluorocarbon polymer having sulfonic acid type functional group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06199958A true JPH06199958A (en) | 1994-07-19 |
| JP3356474B2 JP3356474B2 (en) | 2002-12-16 |
Family
ID=18469720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36051192A Expired - Lifetime JP3356474B2 (en) | 1992-12-28 | 1992-12-28 | Method for producing perfluorocarbon polymer having sulfonic acid type functional group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3356474B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06322034A (en) * | 1993-01-14 | 1994-11-22 | E I Du Pont De Nemours & Co | Polymerization of fluorinated copolymer |
| WO2002051875A1 (en) * | 2000-12-22 | 2002-07-04 | Daikin Industries, Ltd. | Process for producing fluoropolymers |
| WO2009133902A1 (en) * | 2008-04-28 | 2009-11-05 | 旭硝子株式会社 | Method for producing fluorine-containing polymer and fluorine-containing ion exchange membrane |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018235911A1 (en) | 2017-06-21 | 2018-12-27 | Ａｇｃ株式会社 | Method for producing fluorine-containing polymer, fluorine-containing polymer having functional group and electrolyte membrane |
-
1992
- 1992-12-28 JP JP36051192A patent/JP3356474B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06322034A (en) * | 1993-01-14 | 1994-11-22 | E I Du Pont De Nemours & Co | Polymerization of fluorinated copolymer |
| WO2002051875A1 (en) * | 2000-12-22 | 2002-07-04 | Daikin Industries, Ltd. | Process for producing fluoropolymers |
| US7034094B2 (en) | 2000-12-22 | 2006-04-25 | Daikin Industries, Ltd. | Process for preparing fluorine-containing polymer |
| WO2009133902A1 (en) * | 2008-04-28 | 2009-11-05 | 旭硝子株式会社 | Method for producing fluorine-containing polymer and fluorine-containing ion exchange membrane |
| EP2272877A1 (en) * | 2008-04-28 | 2011-01-12 | Asahi Glass Company, Limited | Method for producing fluorine-containing polymer and fluorine-containing ion exchange membrane |
| EP2272877A4 (en) * | 2008-04-28 | 2011-07-06 | Asahi Glass Co Ltd | Method for producing fluorine-containing polymer and fluorine-containing ion exchange membrane |
| US8377998B2 (en) | 2008-04-28 | 2013-02-19 | Asahi Glass Company, Limited | Process for producing fluoropolymer, and fluorinated ion exchange membrane |
| JP5482652B2 (en) * | 2008-04-28 | 2014-05-07 | 旭硝子株式会社 | Method for producing fluoropolymer and fluorine-containing ion exchange membrane |
| TWI447151B (en) * | 2008-04-28 | 2014-08-01 | Asahi Glass Co Ltd | Production method of fluorine-containing polymer and fluorine-containing ion exchange membrane |
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| Publication number | Publication date |
|---|---|
| JP3356474B2 (en) | 2002-12-16 |
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