JPH043410B2 - - Google Patents
Info
- Publication number
- JPH043410B2 JPH043410B2 JP58220193A JP22019383A JPH043410B2 JP H043410 B2 JPH043410 B2 JP H043410B2 JP 58220193 A JP58220193 A JP 58220193A JP 22019383 A JP22019383 A JP 22019383A JP H043410 B2 JPH043410 B2 JP H043410B2
- Authority
- JP
- Japan
- Prior art keywords
- fluoride
- sulfonic acid
- terminal
- reaction
- integer
- 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.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 claims description 22
- 229920001774 Perfluoroether Polymers 0.000 claims description 15
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 14
- -1 perfluorovinyl group Chemical group 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 4
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 2
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DAFIBNSJXIGBQB-UHFFFAOYSA-N perfluoroisobutene Chemical compound FC(F)=C(C(F)(F)F)C(F)(F)F DAFIBNSJXIGBQB-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
本発明は、パーフルオロエーテルスルホン酸重
合体およびその製造法に関する。更に詳しくは、
パーフルオロエーテルスルホン酸フロライドから
導かれる新規なパーフルオロエーテルスルホン酸
重合体およびその製造法に関する。
式
で表わされるパーフルオロエーテルスルホン酸フ
ロライドの末端基をパーフルオロビニル基に変換
して、式
で表わされる末端パーフルオロビニル化合物を製
造することは、米国特許第3282875号明細書に記
載されている。
かかる末端パーフルオロビニル化合物を特定の
触媒の存在下で反応させると、それの重合体たる
末端スルホニルフロライド基含有パーフルオロエ
ーテルスルホン酸重合体が、新規物質として得ら
れることが見出された。また、かかる新規物質重
合体は、末端パーフルオロビニル化合物の合成原
料たる上記パーフルオロエーテルスルホン酸フロ
ライドを、他の特定の触媒の存在下で反応させる
ことによつても、それから直接に得られることが
見出された。そして、このようにして得られた末
端スルホニルフロライド基含有パーフルオロエー
テルスルホン酸重合体をパーフルオロオレフイン
と反応させると、末端フロライド基がパーフルオ
ロアルキル基に変換されたパーフルオロエーテル
スルホン酸重合体が得られることが見出された。
従つて、本発明は、次の一般式で表わされる新
規物質たる末端パーフルオロアルキル基含有パー
フルオロエーテルスルホン酸重合体に係る。
（ここで、R1〜R4はフツ素原子またはパーフル
オロアルキル基であり、ｎは１〜５の整数であ
り、そしてｍは０〜10の整数である）
本発明はまた、かかる末端パーフルオロアルキ
ル基含有パーフルオロエーテルスルホン酸重合体
の製造法に係り、重合体の製造は、一般式
（ここで、ｎは１〜５の整数であり、そしてｍは
０〜10の整数である）で表わされる末端スルホニ
ルフロライド基含有パーフルオロエーテルスルホ
ン酸重合体をパーフルオロオレフインと反応させ
ることにより行われる。
末端スルホニルフロライド基含有パーフルオロ
エーテルスルホン酸重合体〔〕は、次のような
方法によつて製造される。
(1)一般式
（ｎ：１〜５）
で表わされる末端パーフルオロビニル化合物
を、アルカリ金属フロライド、アルカリ土類金
属フロライドまたは４級アンモニウムフロライ
ドの存在下に極性溶媒中で重合させる方法
(2)一般式
（ｎ：１〜５）
で表わされる末端酸フロライド化合物を、アル
カリ金属炭酸塩の存在下に極性溶媒中で重合さ
せる方法
このようにして得られる重合体〔〕に、テト
ラフルオロエチレン、ヘキサフルオロプロピレ
ン、オクタフルオロイソブテンなどのパーフルオ
ロオレフインを末端フロライド基に対して等モル
量以上加え、加圧下に約25〜150℃の温度で反応
させることにより、その末端基をパーフルオロア
ルキル化させる。この反応は、単離された重合体
〔〕について行なうこともできるが、重合体
〔〕を製造した重合反応系をそのまま用いて行
なう方法が好ましく、従つてこのパーフルオロア
ルキル化反応と触媒および溶媒を共通にする前記
重合方法(1)の反応系が好適に用いられる。即ち、
触媒としては、フツ化セシウム、フツ化カリウ
ム、フツ化ナトリウム、フツ化リチウムなどのア
ルカリ金属フロライド、フツ化カルシウムなどの
アルカリ土類金属フロライドまたはテトラメチル
アンモニウムフロライド、テトラエチルアンモニ
ウムフロライドなどの４級アンモニウムフロライ
ドが用いられ、また溶媒としては、ジエチレング
リコールジメチルエーテル、テトラエチレングリ
コールジメチルエーテル、アセトニトリル、アニ
ソール、ジメチルホルムアミド、ジメチルアセト
アミド、ジメチルスルホキシド、ヘキサメチルホ
スホルアミド、スルホランなどの極性溶媒が用い
られる。
なお、このような一連の工程によつて得られる
本発明の目的物たる末端パーフルオロアルキル基
含有パーフルオロエーテルスルホン酸重合体
〔〕において、その一般式中ｍで示される重合
度は当然重合体〔〕の重合度によつて左右され
るが、この重合度はそれの重合反応の際における
反応速度、反応温度、極性溶媒の種類、触媒の溶
解性などの諸要因を種々選択することにより、上
昇せしめることができる。
得られた新規重合体は、その他方の端末パーフ
ルオロビニル基をフツ素ガスで処理してパーフル
オロアルキル化し、更に必要に応じて直鎖中の−
SO2−結合を還元して−Ｓ−結合として、極圧添
加剤、潤滑油などとして有効に使用されるパーフ
ルオロエーテル重合体を合成することができ、従
つてかかる重合体合成の中間体として用いること
ができる。
次に、実施例について本発明を説明する。
参考例 １
次式で表わされる末端パーフルオロビニル化合
物
10ｇ、フツ化セシウム0.5ｇおよびジグライム20
ｇの混合物を、80℃で72時間加熱し、反応させ
た。反応溶液を水洗し、フツ化セシウムおよびジ
グライムを除去すると、粘稠な透明液体8.6ｇが
得られた。
〔Ｆ−NMR積分比〕
The present invention relates to a perfluoroether sulfonic acid polymer and a method for producing the same. For more details,
This invention relates to a novel perfluoroethersulfonic acid polymer derived from perfluoroethersulfonic acid fluoride and a method for producing the same. formula By converting the terminal group of perfluoroether sulfonic acid fluoride represented by the formula into a perfluorovinyl group, the formula The preparation of perfluorovinyl-terminated compounds of the formula is described in US Pat. No. 3,282,875. It has been discovered that when such a terminal perfluorovinyl compound is reacted in the presence of a specific catalyst, a perfluoroether sulfonic acid polymer containing a terminal sulfonyl fluoride group, which is a polymer thereof, can be obtained as a new substance. Furthermore, the new substance polymer can also be obtained directly from the perfluoroether sulfonic acid fluoride, which is a raw material for the synthesis of the terminal perfluorovinyl compound, by reacting it in the presence of other specific catalysts. was discovered. When the thus obtained perfluoroether sulfonic acid polymer containing a terminal sulfonyl fluoride group is reacted with perfluoroolefin, a perfluoroether sulfonic acid polymer in which the terminal fluoride group is converted to a perfluoroalkyl group is obtained. was found to be obtained. Therefore, the present invention relates to a perfluoroether sulfonic acid polymer containing a terminal perfluoroalkyl group, which is a new substance represented by the following general formula. (Here, R 1 to R 4 are fluorine atoms or perfluoroalkyl groups, n is an integer of 1 to 5, and m is an integer of 0 to 10.) Regarding the method for producing a fluoroalkyl group-containing perfluoroether sulfonic acid polymer, the production of the polymer is performed using the general formula (where n is an integer of 1 to 5, and m is an integer of 0 to 10) by reacting a perfluoroether sulfonic acid polymer containing a terminal sulfonyl fluoride group with perfluoroolefin. It will be done. The perfluoroether sulfonic acid polymer containing a terminal sulfonyl fluoride group is produced by the following method. (1) General formula Method (2) of polymerizing a terminal perfluorovinyl compound represented by (n: 1 to 5) in a polar solvent in the presence of an alkali metal fluoride, an alkaline earth metal fluoride, or a quaternary ammonium fluoride A method of polymerizing a terminal acid fluoride compound represented by (n: 1 to 5) in a polar solvent in the presence of an alkali metal carbonate. , perfluoroolefin such as octafluoroisobutene is added in an equimolar amount or more to the terminal fluoride group, and the terminal group is perfluoroalkylated by reacting under pressure at a temperature of about 25 to 150°C. Although this reaction can be carried out on an isolated polymer [], it is preferable to carry out the reaction using the polymerization reaction system used to produce the polymer [] as it is. The reaction system of the polymerization method (1) which shares the following is preferably used. That is,
Examples of catalysts include alkali metal fluorides such as cesium fluoride, potassium fluoride, sodium fluoride, and lithium fluoride, alkaline earth metal fluorides such as calcium fluoride, or quaternary metal fluorides such as tetramethylammonium fluoride and tetraethylammonium fluoride. Ammonium fluoride is used, and as the solvent, polar solvents such as diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, acetonitrile, anisole, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, and sulfolane are used. In addition, in the perfluoroether sulfonic acid polymer containing a terminal perfluoroalkyl group, which is the object of the present invention and is obtained by such a series of steps, the degree of polymerization represented by m in the general formula naturally corresponds to that of the polymer. The degree of polymerization depends on the degree of polymerization of [], and this degree of polymerization is determined by selecting various factors such as the reaction rate, reaction temperature, type of polar solvent, and solubility of the catalyst during the polymerization reaction. It can be made to rise. In the obtained new polymer, the other terminal perfluorovinyl group is treated with fluorine gas to perfluoroalkylate it, and if necessary, -
By reducing SO 2 - bonds to -S- bonds, perfluoroether polymers that are effectively used as extreme pressure additives, lubricants, etc. can be synthesized, and therefore, they can be used as intermediates in the synthesis of such polymers. Can be used. Next, the present invention will be explained with reference to examples. Reference Example 1 Terminal perfluorovinyl compound represented by the following formula 10g, cesium fluoride 0.5g and diglyme 20
The mixture of g was heated at 80° C. for 72 hours to react. The reaction solution was washed with water to remove cesium fluoride and diglyme, and 8.6 g of a viscous transparent liquid was obtained. [F-NMR integral ratio]
1470990cm-1（−SO2F）：相対強度が小さくなる
1420cm-1（−SO2−）：新たに発現
1830cm-1（−CF＝CF2）：減少する
〔GC／MS（ガスクロマトグラフイ／質量分析）〕
873（Ｍ−19）、527、349
〔元素分析値〕
C14F28O8S2としての
計算値 Ｃ：18.8％、Ｆ：59.6％、Ｓ：7.17％
実測値 Ｃ：19.4％、Ｆ：58.9％、Ｓ：7.15％
〔分子量〕
892（GC／MSによる）
〔粘度〕
4.2センチストークス（30℃）
以上の結果から、次のような反応式を考えるこ
とができる。
（前記式〔〕において、ｎ＝１、ｍ＝０）
参考例 ２
次式で表わされる末端酸フロライド化合物
50ｇを、炭酸カリウム74ｇを分散させたジグライ
ム100ml中に、室温下に滴下した。滴下終了後、
130℃で３時間加熱して反応させた。反応混合物
から、釜温200℃、圧力0.1Torrでの留出物を留
去し、粘稠な残渣102ｇを得た。これについて、
トリフルオロトリクロルエタン抽出およびその溶
媒の留去を行ない、粘稠な透明液体41ｇを得た。
〔Ｆ−NMR積分比〕
1470990cm -1 (-SO 2 F): The relative intensity decreases 1420cm -1 (-SO 2 -): Newly expressed 1830cm -1 (-CF=CF 2 ): Decrease [GC/MS (gas chromatography/ Mass spectrometry)] 873 (M-19), 527, 349 [Elemental analysis value] Calculated value as C 14 F 28 O 8 S 2 C: 18.8%, F: 59.6%, S: 7.17% Actual value C: 19.4 %, F: 58.9%, S: 7.15% [Molecular weight] 892 (by GC/MS) [Viscosity] 4.2 centistokes (30°C) From the above results, the following reaction formula can be considered. (In the above formula [], n = 1, m = 0) Reference example 2 Terminal acid fluoride compound represented by the following formula 50g of the solution was dropped at room temperature into 100ml of diglyme in which 74g of potassium carbonate was dispersed. After the dripping is finished,
The reaction was carried out by heating at 130°C for 3 hours. The distillate was distilled off from the reaction mixture at a pot temperature of 200° C. and a pressure of 0.1 Torr to obtain 102 g of a viscous residue. about this,
Extraction with trifluorotrichloroethane and distillation of the solvent were performed to obtain 41 g of a viscous transparent liquid. [F-NMR integral ratio]
1870cm-1（−COF）：消滅する
1470、990cm-1（−SO2F）：減少する
1420cm-1（−SO2−）：新たに発現する
以上の結果から、次のような反応生成物を考え
ることができる。
（前記式〔〕において、ｎ＝１、ｍ＝1.5）
実施例 １
参考例１で用いられた末端パーフルオロビニル
化合物50ｇ、フツ化セシウム2.5ｇおよびジグラ
イム100ｇを、容量200mlのオートクレーブ中に仕
込み、そこにヘキサフルオロプロピレン15ｇを圧
入し、80℃で24時間反応させた。反応終了後、反
応混合物を水洗し、低沸点成分（ヘキサフルオロ
プロピレンの２〜３量体）を留去した。残渣とし
てシロツプ状の物質44.1ｇが得られた。
〔Ｆ−NMR積分比〕
1870cm -1 (-COF): disappears 1470, 990cm -1 (-SO 2 F): decreases 1420cm -1 (-SO 2 -): newly appears From the above results, the following reaction products can be considered. (In the above formula [], n = 1, m = 1.5) Example 1 50 g of the terminal perfluorovinyl compound used in Reference Example 1, 2.5 g of cesium fluoride, and 100 g of diglyme were charged into an autoclave with a capacity of 200 ml, 15 g of hexafluoropropylene was pressurized into the solution, and the mixture was reacted at 80° C. for 24 hours. After the reaction was completed, the reaction mixture was washed with water, and low-boiling components (dimers and trimers of hexafluoropropylene) were distilled off. 44.1 g of a syrupy substance was obtained as a residue. [F-NMR integral ratio]
1470、990cm-1（−SO2F）：消滅する 1420cm-1（−SO2−）：新たに発現する 1830cm-1（−CF＝CF2）：減少する 〔GC／MS〕 527： 499： 1470, 990cm -1 (-SO 2 F): Disappears 1420cm -1 (-SO 2 -): Newly appears 1830cm -1 (-CF=CF 2 ): Decrease [GC/MS] 527: 499:
C17F34O8S2としての
計算値 Ｃ：19.58％、Ｆ：62.00％、
Ｓ：6.14％
実測値 Ｃ：20.1 ％、Ｆ％61.6 ％、
Ｓ：6.82％
〔分子量〕
1042（GC／MSによる）
〔粘度〕
4.7センチストークス（30℃）
以上の結果から、次のような反応式を考えるこ
とができる。
（前記式〔〕において、ｎ＝１、ｍ＝０）
実施例 ２
実施例１において、ヘキサフルオロプロピレン
の代りにテトラフルオロエチレンが10ｇ用いられ
た。その結果、シロツプ状の物質38ｇが得られ
た。
実施例 ３
実施例１において、ヘキサフルオロプロピレン
の代りにオクタフルオロイソブテンが20ｇ用いら
れた。その結果、シロツプ状の物質48ｇが得られ
た。
実施例 ４
実施例１において、フツ化セシウムの代りに同
量のテトラエチルアンモニウムフロライドを用い
ると、シロツプ状の物質が46.3ｇ得られた。
実施例 ５
実施例２において、フツ化セシウムの代りに同
量のテトラエチルアンモニウムフロライドを用い
ると、シロツプ状の物質が38.7ｇ得られた。
実施例 ６
実施例３において、フツ化セシウムの代りに同
量のテトラエチルアンモニウムフロライドを用い
ると、シロツプ状の物質が46.8ｇ得られた。
Calculated value as C 17 F 34 O 8 S 2 C: 19.58%, F: 62.00%, S: 6.14% Actual value C: 20.1%, F% 61.6%, S: 6.82% [Molecular weight] 1042 (GC/MS ) [Viscosity] 4.7 centistokes (30℃) From the above results, the following reaction formula can be considered. (In the above formula [], n=1, m=0) Example 2 In Example 1, 10 g of tetrafluoroethylene was used instead of hexafluoropropylene. As a result, 38 g of a syrupy substance was obtained. Example 3 In Example 1, 20 g of octafluoroisobutene was used instead of hexafluoropropylene. As a result, 48 g of syrup-like material was obtained. Example 4 When the same amount of tetraethylammonium fluoride was used in place of cesium fluoride in Example 1, 46.3 g of syrup-like material was obtained. Example 5 In Example 2, when the same amount of tetraethylammonium fluoride was used in place of cesium fluoride, 38.7 g of syrup-like material was obtained. Example 6 In Example 3, when the same amount of tetraethylammonium fluoride was used in place of cesium fluoride, 46.8 g of syrup-like material was obtained.
Claims (1)
オロアルキル基であり、ｎは１〜５の整数であ
り、そしてｍは０〜10の整数である）で表わされ
る末端パーフルオロアルキル基含有パーフルオロ
エーテルスルホン酸重合体。 ２ 一般式 （ここで、ｎは１〜５の整数であり、そしてｍは
０〜10の整数である）で表わされる末端スルホニ
ルフロライド基含有パーフルオロエーテルスルホ
ン酸重合体を、アルカリ金属またはアルカリ土類
金属のフロライド、あるいは４級アンモニウムフ
ロライドの存在下で、パーフルオロオレフインと
反応させることを特徴とする末端パーフルオロア
ルキル基含有パーフルオロエーテルスルホン酸重
合体の製造法。 ３ 極性溶媒中で反応が行われる特許請求の範囲
第２項記載のパーフルオロエーテルスルホン酸重
合体の製造法。[Claims] 1. General formula (wherein R 1 to R 4 are fluorine atoms or perfluoroalkyl groups, n is an integer of 1 to 5, and m is an integer of 0 to 10) Contains perfluoroether sulfonic acid polymer. 2 General formula (Here, n is an integer of 1 to 5, and m is an integer of 0 to 10). A method for producing a perfluoroether sulfonic acid polymer containing a terminal perfluoroalkyl group, which comprises reacting it with a perfluoroolefin in the presence of a fluoride or a quaternary ammonium fluoride. 3. The method for producing a perfluoroether sulfonic acid polymer according to claim 2, wherein the reaction is carried out in a polar solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58220193A JPS60112829A (en) | 1983-11-22 | 1983-11-22 | Perfluoroethersulfonic acid polymer and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58220193A JPS60112829A (en) | 1983-11-22 | 1983-11-22 | Perfluoroethersulfonic acid polymer and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60112829A JPS60112829A (en) | 1985-06-19 |
| JPH043410B2 true JPH043410B2 (en) | 1992-01-23 |
Family
ID=16747339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58220193A Granted JPS60112829A (en) | 1983-11-22 | 1983-11-22 | Perfluoroethersulfonic acid polymer and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60112829A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1673597A (en) | 1996-03-29 | 1997-10-22 | Daikin Industries, Ltd. | Process for fluorinating cellulosic materials and fluorinated cellulosic materials |
-
1983
- 1983-11-22 JP JP58220193A patent/JPS60112829A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60112829A (en) | 1985-06-19 |
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