JPH06184244A - Production of perfluorocarbon polymer - Google Patents
Production of perfluorocarbon polymerInfo
- Publication number
- JPH06184244A JPH06184244A JP4356039A JP35603992A JPH06184244A JP H06184244 A JPH06184244 A JP H06184244A JP 4356039 A JP4356039 A JP 4356039A JP 35603992 A JP35603992 A JP 35603992A JP H06184244 A JPH06184244 A JP H06184244A
- Authority
- JP
- Japan
- Prior art keywords
- acid type
- sulfonic acid
- functional group
- perfluorocarbon
- monomer
- 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新規な製造方法に
関するものである。FIELD OF THE INVENTION The present invention relates to a novel method for producing a perfluorocarbon polymer having a sulfonic acid type functional group.
【０００２】[0002]
【従来の技術】従来、テトラフルオロエチレンの如き含
フッ素モノマーの水を媒体とする乳化重合においては、
Ｃ7 Ｆ15ＣＯ2 ＮＨ4 、Ｃ8 Ｆ17ＣＯ2 ＮＨ4 などのパ
ーフルオロカルボン酸型乳化剤を用いる重合系が採用さ
れている。そして、ＣＦ2 ＝ＣＦＯ（ＣＦ2)3 ＣＯ2 Ｃ
Ｈ3 の如きカルボン酸型官能基を有するパーフルオロカ
ーボンモノマーとＣＦ2 ＝ＣＦ2 などとの共重合におい
ても、同様のパーフルオロカルボン酸型乳化剤が用いら
れており、乳化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が有利に製造されている。2. Description of the Related Art Conventionally, in the emulsion polymerization of a fluorine-containing monomer such as tetrafluoroethylene with water as a medium,
Polymerization systems using perfluorocarboxylic acid type emulsifiers such as C 7 F 15 CO 2 NH 4 and C 8 F 17 CO 2 NH 4 have been adopted. And CF 2 = CFO (CF 2 ) 3 CO 2 C
The same perfluorocarboxylic acid type emulsifier is also used in the copolymerization of perfluorocarbon monomer having a carboxylic acid type functional group such as H 3 and CF 2 ═CF 2, etc., and a high ion exchange capacity is obtained by emulsion copolymerization. Advantageously, the perfluorocarbon polymers of
【０００３】一方、ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3)
ＯＣＦ2 ＣＦ2 ＳＯ2 Ｆの如きスルホン酸型官能基を有
するパーフルオロカーボンモノマーとＣＦ2 ＝ＣＦ2 な
どとの共重合において、高イオン交換容量を達成するた
めには、重合媒体を使用しない塊状重合、あるいはトリ
クロロトリフルオロエタンの如き、フッ素系溶剤を媒体
とする溶液重合が採用されている。On the other hand, CF 2 = CFOCF 2 CF (CF 3 ).
In the copolymerization of CF 2 ═CF 2 and the like with a perfluorocarbon monomer having a sulfonic acid type functional group such as OCF 2 CF 2 SO 2 F, in order to achieve a high ion exchange capacity, bulk polymerization without using a polymerization medium is performed. Alternatively, solution polymerization using a fluorine-based solvent as a medium such as trichlorotrifluoroethane is adopted.
【０００４】スルホン酸型モノマーとＣＦ2 ＝ＣＦ2 な
どとの共重合に水媒体中乳化重合を採用する方法も、文
献上では一般に知られている。しかし、本発明者の研究
によれば、従来のパーフルオロカルボン酸型乳化剤を用
いた乳化重合においては、イオン交換容量の極めて低い
ものしか得られず、イオン交換膜の原料などとして用い
る場合の少なくとも０．５ミリ当量／グラム乾燥樹脂を
達成することが非常に難しいことが判明した。A method of employing emulsion polymerization in an aqueous medium for copolymerization of a sulfonic acid type monomer and CF 2 ═CF 2 etc. is also generally known in the literature. However, according to the study of the present inventor, in the conventional emulsion polymerization using a perfluorocarboxylic acid type emulsifier, only an extremely low ion exchange capacity is obtained, and at least when used as a raw material for an ion exchange membrane. It has been found very difficult to achieve 0.5 meq / g dry resin.
【０００５】その解決方法として、超音波（特開昭６０
−２５０００９号）やホモジナイザー（特開昭６２−２
８８６１７号）を用い、予めスルホン酸型モノマーを乳
化した後共重合する方法や、特殊な乳化剤を用いる方法
（特開昭６２−２８８６１４号、特開昭６２−２８８６
１５号、特開昭６２−２８８６１６号）が提案されてい
る。しかし、予め乳化する方法では製造工程が繁雑にな
り、また特殊な乳化剤を使用する方法は、これらの乳化
剤が通常のパーフルオロカルボン酸型乳化剤に比べ高価
であり、使用量も多く、製造コストが上昇する等の問題
点があった。As a method for solving the problem, ultrasonic waves (Japanese Patent Laid-Open No. Sho 60) are used.
-250009) and a homogenizer (JP-A-62-2).
No. 88617), a method of emulsifying a sulfonic acid type monomer in advance and then copolymerizing it, and a method of using a special emulsifier (JP-A-62-288614, JP-A-62-2886).
No. 15, JP-A No. 62-288616). However, the method of emulsifying in advance complicates the manufacturing process, and the method of using a special emulsifier is expensive as compared with a normal perfluorocarboxylic acid type emulsifier, and the amount of the emulsifier used is large and the manufacturing cost is high. There were problems such as rising prices.
【０００６】[0006]
【発明が解決しようとする課題】本発明は水性媒体中、
重合開始源の作用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とパーフルオロオレフィンとを
乳化共重合せしめる方法により、イオン交換容量の大き
いパーフルオロカーボン重合体を高収率で容易に製造す
る方法を提供する。DISCLOSURE OF THE INVENTION The present invention relates to an aqueous medium,
Provided is a method for easily producing a perfluorocarbon polymer having a large ion exchange capacity in a high yield by a method of emulsion-copolymerizing a perfluorocarbon monomer containing a sulfonic acid type functional group and a perfluoroolefin by the action of a polymerization initiation source. .
【０００７】[0007]
【課題を解決するための手段】本発明は、上記課題を解
決しようとするものであり、水性媒体中、重合開始源の
作用によりスルホン酸型官能基含有パーフルオロカーボ
ンとパーフルオロオレフィンとを乳化共重合せしめる方
法において、含フッ素乳化剤を用い、かつ水溶性有機溶
媒を添加することを特徴とするパーフルオロカーボン共
重合体の製造方法にある。DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and comprises emulsifying a perfluorocarbon containing a sulfonic acid type functional group and a perfluoroolefin in an aqueous medium by the action of a polymerization initiation source. In the method of polymerizing, there is provided a method for producing a perfluorocarbon copolymer, which comprises using a fluorine-containing emulsifier and adding a water-soluble organic solvent.
【０００８】本発明の方法において、含フッ素乳化剤と
しては、従来よりテトラフルオロエチレンその他の含フ
ッ素モノマーの乳化重合において使用されるものが広く
使用できる。例えば、Ｃ7 Ｆ15ＣＯ2 ＮＨ4 、Ｃ8 Ｆ17
ＣＯ2 ＮＨ4 の如きパーフルオロカルボン酸型乳化剤、
Ｃ8 Ｆ17ＳＯ3 ＮＨ4 の如きパーフルオロスルホン酸型
乳化剤、Ｃ2 Ｆ5 ［ＣＦ2 ＯＣＦ（ＣＦ3 ）］3 ＣＯ2
ＮＨ4 の如きパーフルオロエーテルカルボン酸型乳化剤
等が使用できる。これらは、カリウム塩型やナトリウム
塩型も使用できるが、入手が容易で、安価かつ乳化効果
の高いＮＨ4 型の使用が好ましい。In the method of the present invention, as the fluorine-containing emulsifier, those conventionally used in emulsion polymerization of tetrafluoroethylene and other fluorine-containing monomers can be widely used. For example, C 7 F 15 CO 2 NH 4 , C 8 F 17
Perfluorocarboxylic acid type emulsifiers such as CO 2 NH 4 ,
Perfluorosulfonic acid type emulsifiers such as C 8 F 17 SO 3 NH 4 , C 2 F 5 [CF 2 OCF (CF 3 )] 3 CO 2
Perfluoroethercarboxylic acid type emulsifiers such as NH 4 can be used. Although potassium salt type and sodium salt type can be used, NH 4 type, which is easily available, inexpensive and has a high emulsifying effect, is preferable.
【０００９】かかる含フッ素乳化剤の使用量は水性媒体
中０．０１〜５重量％、好ましくは０．０５〜２．０重
量％程度の濃度で使用され得る。The amount of such a fluorine-containing emulsifier to be used may be 0.01 to 5% by weight, preferably 0.05 to 2.0% by weight, in the aqueous medium.
【００１０】また、本発明で使用される水溶性有機溶媒
としては好ましくは分子式中に酸素を有する水溶性有機
溶媒、例えばエタノール、プロパノール、ブタノールの
如き低級アルコール、アセトン、メチルエチルケトンの
如きケトン、テトラヒドロフラン、ジオキサンの如きエ
ーテルが使用される。なかでも分子量の大きいスルホン
酸型官能基含有パーフルオロカーボン重合体が得られる
ことからプロパノール、ターシャリーブタノール、アセ
トン等、特にターシャリーブタノールの使用が好まし
い。The water-soluble organic solvent used in the present invention is preferably a water-soluble organic solvent having oxygen in its molecular formula, for example, lower alcohols such as ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, Ethers such as dioxane are used. Among them, propanol, tert-butanol, acetone and the like, especially tert-butanol are particularly preferable because a sulfonic acid type functional group-containing perfluorocarbon polymer having a large molecular weight can be obtained.
【００１１】かかる水溶性有機溶媒の添加量としては、
水性媒体中に対し、２〜２５重量％用いられる。これよ
り少ないと効果が乏しく、多いと生成乳化粒子が破壊さ
れる場合がある。より好ましくは５〜２０重量％用いら
れる。The amount of the water-soluble organic solvent added is
It is used in an amount of 2 to 25% by weight based on the aqueous medium. If it is less than the above range, the effect is poor, and if it is more than the above range, the generated emulsion particles may be destroyed. More preferably, it is used in an amount of 5 to 20% by weight.
【００１２】本発明において重合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、広範
囲にわたって例示され得る。好適なものとしては、一般
式ＣＦ2 ＝ＣＦ−（ＯＣＦ2 ＣＦＸ)p−（Ｏ)q−（ＣＦ
2)r −（ＣＦ2 ＣＦＺ)s−Ａ（式中、ｐは０〜３、ｑは
０又は１、ｒは０〜１２、ｓは０〜１２であり、Ｘは−
Ｆ又は−ＣＦ3 であり、Ｚ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。通常は
入手容易性などの点から、Ｘ及びＺは−ＣＦ3、ｐ，ｑ
は０又は１、ｒは０〜８、ｓは０であり、またＡは共重
合反応性などから−ＳＯ2 Ｆが好ましい。The sulfonic acid type functional group-containing perfluorocarbon monomer to be polymerized in the present invention can be exemplified in a wide range. Preferable examples of the general formula CF 2 = CF- (OCF 2 CFX ) p - (O) q - (CF
2) r - (in CF 2 CFZ) s -A (wherein, p is 0 to 3, q is 0 or 1, r is 0 to 12, s is 0 to 12, X is -
F or -CF 3, Z is -F or -CF 3,
A is a sulfonic acid type functional group). Usually, X and Z are —CF 3 , p, q from the viewpoint of easy availability.
Is 0 or 1, r is 0 to 8, s is 0, and A is preferably —SO 2 F from the viewpoint of copolymerization reactivity.
【００１３】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)1-8 ＳＯ2 Ｆ, ＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3)Ｏ（ＣＦ2)1-8 ＳＯ
2 Ｆ, ＣＦ2 ＝ＣＦ（ＣＦ2)0-8 ＳＯ2 Ｆ, ＣＦ2 ＝ＣＦ［ＯＣＦ2 ＣＦ（ＣＦ3)]1-5ＳＯ2 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 SO
2 F, CF 2 = CF ( CF 2) 0-8 SO 2 F, CF 2 = CF [OCF 2 CF (CF 3)] 1-5 SO 2 F , and the like.
【００１４】本発明においては、パーフルオロオレフィ
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水性媒体中で乳化共重合せしめられ
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 ＝ＣＦＯＲf
（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, the perfluoroolefin and the sulfonic acid type functional group-containing perfluorocarbon monomer as described above can be emulsion-copolymerized in an aqueous medium, but two or more sulfonic acid type functional group-containing perfluorocarbon monomers can be used. In addition to these monomers, other components such as carboxylic acid type functional group-containing perfluorocarbon monomer, CF 2 ═CFOR f
(R f represents a perfluoroalkyl group having 1 to 10 carbon atoms), or CF 2 ═CF—CF═CF 2 , CF 2 ═
One or more divinyl monomers such as CFO (CF 2 ) 1-4 OCF = CF 2 may be used in combination.
【００１５】しかして、本発明においては、水性媒体中
の乳化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 the object is a perfluorocarbon polymer in which a high proportion of sulfonic acid type functional group-containing perfluorocarbon monomer is copolymerized by emulsion copolymerization in an aqueous medium, the sulfonic acid is usually used. In order to produce a perfluorocarbon polymer in which the copolymerization ratio of the type functional group-containing perfluorocarbon monomer is 20% by weight or more, it is desirable to select the use ratio of the above various monomers. In particular, the copolymerization ratio of the sulfonic acid type functional group-containing perfluorocarbon monomer is 25 to
It is preferably selected so as to produce about 60% by weight of a perfluorocarbon polymer.
【００１６】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を大きくでき
る。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。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１７０〜３４０℃、特に１８０〜２８０℃程度
とするのが好適である。When the sulfonic acid type perfluorocarbon polymer obtained according to 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 can be increased. 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. The molecular weight of the sulfonic acid type perfluorocarbon polymer obtained in the present invention, since the relationship between mechanical performance and film formability as an ion-exchange membrane is important, when viewed in the value of T Q, 0.99 ° C. or higher, The temperature is preferably 170 to 340 ° C, and more preferably 180 to 280 ° C.
【００１７】本発明中において「ＴQ 」なる言葉は、次
のように定義される。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、容量流速は、共重合体を３０ｋｇ／ｃｍ2 加圧下、
一定温度で径１ｍｍ、長さ２ｍｍのオリフィスから熔融
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 the present invention, the term "T Q " is defined as follows. That is, the temperature showing a volumetric flow rate of 100 mm 3 / sec, which is related to the molecular weight of the copolymer, is defined as T Q, and the volumetric flow rate of the copolymer is 30 kg / cm 2 under pressure.
The figure shows the amount of copolymer flowing out from an orifice having a diameter of 1 mm and a length of 2 mm at a constant temperature, and the amount of the copolymer flowing out is in units of mm 3 / sec.
【００１８】また、「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.
【００１９】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、水性媒体の使用量を水性媒体／官能性単量体の
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。水性媒体の使用量
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。ここで
水性媒体とは水と水溶性溶媒の混合物を表わす。In the present invention, the copolymerization reaction of a functional monomer such as a sulfonic acid type monomer with a perfluoroolefin is carried out by using an aqueous medium in an amount of 20/1 by weight ratio of aqueous medium / functional monomer. It is preferable to carry out the treatment at a controlled temperature of 10/1 or less. When the amount of the aqueous medium used is too large, there are disadvantages in work operation such as enlargement of the reactor or separation and recovery of the copolymer. Here, the aqueous medium represents a mixture of water and a water-soluble solvent.
【００２０】次に、本発明においては、２ｋｇ／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。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、５０ｋｇ／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２〜５０ｋｇ／ｃｍ2 、好ましく
は４〜３０ｋｇ／ｃｍ2 の範囲から選定するのが最適で
ある。Next, in the present invention, 2 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. Incidentally, the copolymerization reaction pressure is preferably selected from 50 kg / cm 2 or less in consideration of the reaction apparatus or the work operation in industrial practice. 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 optimally selected from the range of 2 to 50 kg / cm 2 , preferably 4 to 30 kg / cm 2 .
【００２１】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、１０〜９０℃、好ましく
は２０〜８０℃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, as the copolymerization reaction temperature, an optimum value can be selected depending on the kind of the weight initiation source, the reaction molar ratio, etc. However, usually, too high temperature or too low temperature is disadvantageous for industrial practice, and therefore 10 to 90 C., preferably about 20 to 80.degree.
【００２２】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。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.
【００２３】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１０〜９０℃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、過硫酸カリウム、過硫酸アンモニ
ウム等の無機過酸化物及びそれらのレドックス系等であ
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 10 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, peroxydicarbonates such as di-2-ethylhexyl peroxydicarbonate, hydroperoxides such as diisopropylbenzene hydroperoxide, inorganic peroxides such as potassium persulfate and ammonium persulfate, and redox systems thereof. Etc.
【００２４】本発明においては、重合開始源の濃度は、
全モノマーに対して0.0001〜３重量％、好ましくは0.00
01〜２重量％程度である。開始源の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
始源の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装置に対
して不利となる。その他通常の水を媒体とする乳化共重
合において用いられる分散剤、緩衝剤、分子量調整剤等
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 0.00
It is about 1 to 2% by weight. By decreasing the concentration of the starting source, it is possible to increase the molecular weight of the produced copolymer, and it is possible to maintain a high ion exchange capacity. If the concentration of the starting source is too high, the tendency of lowering the molecular weight is increased, which is a disadvantage for a device having a high ion exchange capacity and a high molecular weight copolymer. In addition, a dispersant, a buffering agent, a molecular weight adjusting agent and the like used in ordinary emulsion copolymerization using water as a medium can be added.
【００２５】本発明においては、生成共重合体濃度を４
０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、ラテックスの分散破壊などの難
点が認められる。本発明のスルホン酸型パーフルオロカ
ーボン重量体からイオン交換膜を製造する場合、製膜は
適宜手段にて実施され得る。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。In the present invention, the concentration of the produced copolymer is 4
It is suitable to control the amount to be 0% by weight or less, preferably 30% by weight or less. If the concentration is too high, problems such as increased non-uniformity of copolymer composition and dispersion breakage of latex are observed. When an ion exchange membrane is produced from the sulfonic acid type perfluorocarbon weight body of the present invention, the membrane can be formed 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】本発明の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 of the present invention has various excellent performances and thus can be widely used 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樹脂膜
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。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。For example, the cation exchange resin film as described above divides the anode and the cathode to form an anode chamber and a cathode chamber, and an alkaline chloride aqueous solution is supplied to the anode chamber to electrolyze the cathode chamber. Even in the case of a so-called two-chamber type tank for obtaining alkali hydroxide from a solution, by electrolyzing at a current density of 5 to 50 A / dm 2 using a sodium chloride aqueous solution having a concentration of 2 N or more as a raw material, a high concentration of 30% or more can be obtained. Sodium hydroxide can be stably produced over a long period of time with high current efficiency and low cell voltage. Next, examples of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by the description.
【００２８】[0028]
［実施例１］イオン交換水９０ｇ、ターシャリーブタノ
ール １０ｇ、Ｃ8 Ｆ17ＣＯ2 ＮＨ4 ０．３５ｇ、Ｎａ
2 ＨＰＯ4 ・12Ｈ2 Ｏ ０．５ｇ、ＮａＨ2 ＰＯ4 ・２
Ｈ2Ｏ ０．３０ｇ、（ＮＨ4)2 Ｓ2 Ｏ8 １００ｍｇ、
及びＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3)Ｏ（ＣＦ2)2 Ｓ
Ｏ2 Ｆ ３０ｇ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窒素で充分脱気した後、６
０℃とし、テトラフルオロエチレンを１０ｋｇ／ｃｍ2
迄仕込み重合を開始させた。[Example 1] Ion-exchanged water 90 g, tertiary butanol 10g, C 8 F 17 CO 2 NH 4 0.35g, Na
2 HPO 4 · 12H 2 O 0.5g , NaH 2 PO 4 · 2
H 2 O 0.30g, (NH 4 ) 2 S 2 O 8 100mg,
And CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 S
After charging 30 g of O 2 F into a stainless steel autoclave having an internal volume of 0.2 liter and thoroughly degassing with liquid nitrogen, 6
0 ° C., tetrafluoroethylene 10 kg / cm 2
Up to the start of polymerization.
【００２９】反応中は系外より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。３．６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、得られたラテックスを凝集し、洗浄乾燥を行って２
９．６ｇの共重合体を得た。該共重合体のイオン交換容
量は０．７１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％ＨａＯＨ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。During the reaction, tetrafluoroethylene was introduced from outside the system to keep the pressure constant. After 3.6 hours, unreacted tetrafluoroethylene was purged to terminate the polymerization, and the obtained latex was coagulated, washed and dried to obtain 2
9.6 g of copolymer was obtained. The ion exchange capacity of the copolymer was 0.71 meq / g dry resin. A tough film was obtained by press-forming the copolymer at 250 ° C., and a sulfonic acid type ion-exchange membrane was obtained by hydrolysis with a 25% aqueous NaOH solution.
【００３０】次にイオン交換水１００ｇを用いターシャ
リーブタノールを添加しなかった以外は同様にして重合
し、後処理を行ったところ、得られた共重合体のイオン
交換容量は０．１９ミリ当量／グラム乾燥樹脂以下であ
った。Polymerization and post-treatment were carried out in the same manner except that 100 g of ion-exchanged water was used and no tertiary butanol was added, and the resulting copolymer had an ion-exchange capacity of 0.19 meq. / Gram dry resin or less.
【００３１】［実施例２］イオン交換水８５ｇ、ターシ
ャリーブタノール１５ｇを使用する以外は実施例１と同
様に重合し、後処理を行ったところ、得られた共重合体
のイオン交換容量は１．２２ミリ当量／グラム乾燥樹脂
であった。[Example 2] Polymerization and post-treatment were conducted in the same manner as in Example 1 except that 85 g of ion-exchanged water and 15 g of tertiary butanol were used, and the post-treatment was carried out. .22 meq / g dry resin.
【００３２】［実施例３］乳化剤としてＣ8 Ｆ17ＣＯ2
ＮＨ4 に換えてＣ8 Ｆ17ＳＯ3 ＮＨ4 を用いる以外は実
施例１と同様に重合し、後処理を行ったところ、得られ
た共重合体のイオン交換容量は０．９９ミリ当量／グラ
ム乾燥樹脂であった。[Example 3] C 8 F 17 CO 2 as an emulsifier
But using C 8 F 17 SO 3 NH 4 instead of the NH 4 is polymerized in the same manner as in Example 1, was subjected to post-treatment, ion-exchange capacity of the resulting copolymer was 0.99 meq / It was gram dry resin.
【００３３】［実施例４］イオン交換水９２ｇ、ターシ
ャリーブタノール８ｇを使用し、テトラフルオロエチレ
ンの圧力を８ｋｇ／ｃｍ2 にした以外は実施例１と同様
に重合し、後処理を行ったところ、得られた共重合体の
イオン交換容量は０．９７ミリ当量／グラム乾燥樹脂で
あった。Example 4 Polymerization and post-treatment were carried out in the same manner as in Example 1 except that 92 g of ion-exchanged water and 8 g of tertiary butanol were used and the pressure of tetrafluoroethylene was set to 8 kg / cm 2. The ion exchange capacity of the obtained copolymer was 0.97 meq / g dry resin.
【００３４】[0034]
【発明の効果】本発明は、超音波等の特殊な前処理や特
殊な乳化剤を用いることなく、スルホン酸型官能基の含
有量の大きいパーフルオロカーボン重合体が容易に高収
率で製造できる。INDUSTRIAL APPLICABILITY According to the present invention, a perfluorocarbon polymer having a large sulfonic acid type functional group content can be easily produced in a high yield without using a special pretreatment such as ultrasonic waves or a special emulsifier.
Claims (3)
ホン酸型官能基含有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乳化共重合せしめる方法におい
て含フッ素乳化剤を用い、かつ水溶性有機溶媒を添加す
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. Use of a fluorine-containing emulsifier in a method of emulsion-copolymerizing a perfluorocarbon monomer containing a sulfonic acid type functional group and a perfluoroolefin in an aqueous medium by the action of a polymerization initiation source, and adding a water-soluble organic solvent. A method for producing a perfluorocarbon polymer, comprising:
である請求項１の方法。2. The method according to claim 1, wherein the water-soluble organic solvent is tertiary butanol.
ボンモノマーがＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3 ）Ｏ
ＣＦ2 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テトラフルオロエチレンであ
り、前者の共重合割合が２０重量％以上である請求項１
の方法。3. A sulfonic acid type functional group-containing perfluorocarbon monomer is CF 2 ═CFOCF 2 CF (CF 3 ) O.
2. CF 2 CF 2 SO 2 F, wherein the perfluoroolefin to be copolymerized with it is tetrafluoroethylene, and the former copolymerization ratio is 20% by weight or more.
the method of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35603992A JP3280727B2 (en) | 1992-12-18 | 1992-12-18 | Method for producing perfluorocarbon polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35603992A JP3280727B2 (en) | 1992-12-18 | 1992-12-18 | Method for producing perfluorocarbon polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06184244A true JPH06184244A (en) | 1994-07-05 |
| JP3280727B2 JP3280727B2 (en) | 2002-05-13 |
Family
ID=18447019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35603992A Expired - Fee Related JP3280727B2 (en) | 1992-12-18 | 1992-12-18 | Method for producing perfluorocarbon polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3280727B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995010541A1 (en) * | 1993-10-12 | 1995-04-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Perfluorocarbon copolymer having functional groups and process for producing the same |
| WO1999043723A1 (en) * | 1998-02-27 | 1999-09-02 | Asahi Glass Company Ltd. | Process for producing aqueous dispersion containing polytetrafluoroethylene |
| JP2007119526A (en) * | 2005-10-25 | 2007-05-17 | Asahi Glass Co Ltd | Method for preparing fluorine-containing polymer |
| JP2010037365A (en) * | 2008-07-31 | 2010-02-18 | Daikin Ind Ltd | Preparation method of fluorine-containing polymer |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4929389A (en) * | 1972-07-19 | 1974-03-15 | ||
| JPS4962584A (en) * | 1972-10-20 | 1974-06-18 | ||
| JPS55160008A (en) * | 1979-12-28 | 1980-12-12 | Asahi Chem Ind Co Ltd | Fluorinated copolymer and production thereof |
| JPS5650947A (en) * | 1979-09-26 | 1981-05-08 | Du Pont | Solution of perfluorinated polymer |
| JPS59196308A (en) * | 1983-04-20 | 1984-11-07 | Daikin Ind Ltd | Production of modified polytetrafluoroethylene |
| JPS59206006A (en) * | 1983-03-16 | 1984-11-21 | Daikin Ind Ltd | Separation membrane |
| JPS60250009A (en) * | 1984-05-25 | 1985-12-10 | Asahi Glass Co Ltd | Production of perfluorocarbon polymer having sulfonic acid functional group |
| JPS61223007A (en) * | 1985-03-28 | 1986-10-03 | Daikin Ind Ltd | Emulsion polymerization of fluoroelastomer |
| JPS62285907A (en) * | 1986-06-03 | 1987-12-11 | Asahi Glass Co Ltd | Production of tetrafluoroethylene/fluorovinyl ether copolymer |
| JPS62288614A (en) * | 1986-06-06 | 1987-12-15 | Asahi Glass Co Ltd | Production of perfluorocarbon polymer having sulfonic acid type functional group |
| JPH02182710A (en) * | 1988-11-17 | 1990-07-17 | Ausimont Srl | Manufacture of tetrafluoroethylene/ ethylene copolymer |
| JPH03243608A (en) * | 1990-02-20 | 1991-10-30 | Asahi Glass Co Ltd | Ethylene-tetrafluoroethylene copolymer |
| JPH04106111A (en) * | 1990-08-28 | 1992-04-08 | Dainippon Ink & Chem Inc | Production of fluorocopolymer |
-
1992
- 1992-12-18 JP JP35603992A patent/JP3280727B2/en not_active Expired - Fee Related
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4929389A (en) * | 1972-07-19 | 1974-03-15 | ||
| JPS4962584A (en) * | 1972-10-20 | 1974-06-18 | ||
| JPS5650947A (en) * | 1979-09-26 | 1981-05-08 | Du Pont | Solution of perfluorinated polymer |
| JPS55160008A (en) * | 1979-12-28 | 1980-12-12 | Asahi Chem Ind Co Ltd | Fluorinated copolymer and production thereof |
| JPS59206006A (en) * | 1983-03-16 | 1984-11-21 | Daikin Ind Ltd | Separation membrane |
| JPS59196308A (en) * | 1983-04-20 | 1984-11-07 | Daikin Ind Ltd | Production of modified polytetrafluoroethylene |
| JPS60250009A (en) * | 1984-05-25 | 1985-12-10 | Asahi Glass Co Ltd | Production of perfluorocarbon polymer having sulfonic acid functional group |
| JPS61223007A (en) * | 1985-03-28 | 1986-10-03 | Daikin Ind Ltd | Emulsion polymerization of fluoroelastomer |
| JPS62285907A (en) * | 1986-06-03 | 1987-12-11 | Asahi Glass Co Ltd | Production of tetrafluoroethylene/fluorovinyl ether copolymer |
| JPS62288614A (en) * | 1986-06-06 | 1987-12-15 | Asahi Glass Co Ltd | Production of perfluorocarbon polymer having sulfonic acid type functional group |
| JPH02182710A (en) * | 1988-11-17 | 1990-07-17 | Ausimont Srl | Manufacture of tetrafluoroethylene/ ethylene copolymer |
| JPH03243608A (en) * | 1990-02-20 | 1991-10-30 | Asahi Glass Co Ltd | Ethylene-tetrafluoroethylene copolymer |
| JPH04106111A (en) * | 1990-08-28 | 1992-04-08 | Dainippon Ink & Chem Inc | Production of fluorocopolymer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995010541A1 (en) * | 1993-10-12 | 1995-04-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Perfluorocarbon copolymer having functional groups and process for producing the same |
| US5608022A (en) * | 1993-10-12 | 1997-03-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Perfluorocarbon copolymer containing functional groups and a method for producing it |
| WO1999043723A1 (en) * | 1998-02-27 | 1999-09-02 | Asahi Glass Company Ltd. | Process for producing aqueous dispersion containing polytetrafluoroethylene |
| JP2007119526A (en) * | 2005-10-25 | 2007-05-17 | Asahi Glass Co Ltd | Method for preparing fluorine-containing polymer |
| JP2010037365A (en) * | 2008-07-31 | 2010-02-18 | Daikin Ind Ltd | Preparation method of fluorine-containing polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3280727B2 (en) | 2002-05-13 |
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