JPS6046123B2 - Fluorine-containing copolymer and method for producing the same - Google Patents

Fluorine-containing copolymer and method for producing the same

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Publication number
JPS6046123B2
JPS6046123B2 JP10197576A JP10197576A JPS6046123B2 JP S6046123 B2 JPS6046123 B2 JP S6046123B2 JP 10197576 A JP10197576 A JP 10197576A JP 10197576 A JP10197576 A JP 10197576A JP S6046123 B2 JPS6046123 B2 JP S6046123B2
Authority
JP
Japan
Prior art keywords
copolymer
formula
mol
tfe
polymer
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
Application number
JP10197576A
Other languages
Japanese (ja)
Other versions
JPS5326884A (en
Inventor
孝臣 里川
恒男 藤井
晃 大森
光一郎 上田
清子 三島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Kogyo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Daikin Kogyo Co Ltd filed Critical Daikin Kogyo Co Ltd
Priority to JP10197576A priority Critical patent/JPS6046123B2/en
Publication of JPS5326884A publication Critical patent/JPS5326884A/en
Publication of JPS6046123B2 publication Critical patent/JPS6046123B2/en
Expired legal-status Critical Current

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Description

【発明の詳細な説明】 本発明は新規重合体であるテトラフルオロエチレンとα
・β・β一トリフルオロスチレンとの共重合体およびそ
の製造方法に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention describes novel polymers of tetrafluoroethylene and α
-Relating to a copolymer with β/β-trifluorostyrene and a method for producing the same.

テトラフルオロエチレン(以下TFEと云う)およびα
・β・β一トリフルオロスチレン(以下TFSと云う)
のそれぞれ単独の重合体は公知で・ある。
Tetrafluoroethylene (hereinafter referred to as TFE) and α
・β・β-Trifluorostyrene (hereinafter referred to as TFS)
Each individual polymer is known.

TFE重合体はフッ素樹脂の中でも代表的なものであつ
て、極めて優れた耐熱、耐薬品性および電気特性を有し
て広く使用されている。一方TFE重合体は前者ほど広
く使用されているものではないが製造法や重合体の性質
については知られており、重合体としては軟化温度が高
く (約240℃)、電気的特性が高いと云う特性を有
する。またこれをスルホン化しものは耐熱性イオン交換
樹脂として使用されることが知られている。しかしなが
らTFS重合体のスルホン化物は可撓性が弱くこれをイ
オン交換膜として使用するには実用上多くの問題を有し
ている。本発明者らはTFSのフェニル基がスルホン化
、アミノ化等により種々の官能基により置換される特性
、およびその置換体に種々の有用な用途が期待されるこ
とに注目し、スルホン化等により可撓性の低下しないT
FS成分有含フッ素共重合体の製造を試み本発明を完成
した。
TFE polymers are typical among fluororesins and are widely used because of their extremely excellent heat resistance, chemical resistance, and electrical properties. On the other hand, TFE polymer is not as widely used as the former, but its manufacturing method and polymer properties are known, and as a polymer it has a high softening temperature (approximately 240°C) and good electrical properties. It has the following characteristics. It is also known that sulfonated products are used as heat-resistant ion exchange resins. However, sulfonated TFS polymers have poor flexibility and have many practical problems when used as ion exchange membranes. The present inventors have focused on the property that the phenyl group of TFS can be substituted with various functional groups by sulfonation, amination, etc., and that the substituted products are expected to have various useful applications. T that does not reduce flexibility
The present invention was completed by attempting to produce a fluorine-containing copolymer containing an FS component.

本発明は式:(CF2CF2)および で示される繰り返し単位を、それぞれ5〜95モル%お
よび95〜5モル%の割合で含有し、メチルエチルケト
ン溶液として35℃で測定した極限粘度が少なくとも約
0.1d11fであることを特徴とする共重合体ならび
にその製造方法に関する。
The present invention contains repeating units represented by formula: (CF2CF2) and in proportions of 5 to 95 mol% and 95 to 5 mol%, respectively, and has an intrinsic viscosity of at least about 0.1d11f measured as a methyl ethyl ketone solution at 35°C. The present invention relates to a copolymer characterized by: and a method for producing the same.

本発明のTFEとTFSとの共重合体は新規な重合体で
あつて、耐薬品性、耐熱性が高く、可撓性においても優
れている他、そのフェニル基にスルホン酸基等の官能基
を導入しても、その物性を低下させることがない。
The copolymer of TFE and TFS of the present invention is a new polymer that has high chemical resistance, high heat resistance, and excellent flexibility. Even if introduced, the physical properties will not be deteriorated.

本発明に係る共重合体中のTFE成分の含有量は5〜9
5モル%が好ましい。
The content of TFE component in the copolymer according to the present invention is 5 to 9
5 mol% is preferred.

この共重合体は重合系中にTFEを25〜99モル%存
在させ、ラジカル重合開始源を用いて重合することによ
り製造することができる。本発明に係る共重合体は、メ
チルエチルケトン溶液として35℃で測定して少なくと
も約0.1d1′yの極限粘度を有する。
This copolymer can be produced by including 25 to 99 mol % of TFE in the polymerization system and polymerizing using a radical polymerization initiation source. The copolymers of the present invention have an intrinsic viscosity of at least about 0.1 d1'y, measured as a solution in methyl ethyl ketone at 35°C.

極限粘度がこれより小さいと、共重合体は分子量が低く
、形状保持性が乏しく、またその成型体は脆くなつて実
用的でない。本発明TFE−TFS共重合体はTFEの
含有割合.が高い場合は結晶性が比較的高く、逆にTF
S含有割合が高い場合は結晶性が低下して無定形の重合
体となる。この重合体のとくに顕著な特性はTFS含量
が比較的高いとき、その二次転移点(Tg)が非常に高
くなることである。例えば実施4例に示すごとくTFS
含有量90.7モル%の共重合体の二次転移点は180
℃であり、公知の重合体として比較しても最高のレベル
にある。この共重合体は熱分解温度も350〜450℃
と高く、したがつて成形性において優れている。さらに
またこの共重合・体は本質的に熱可塑性であつて、TF
Eの単独重合体と異り、加熱溶融により押出、射出、圧
縮等任意の方法で成形することができる。しかもアセト
ン、メチルエチルケトン、クロロホルム、ベンゼン、ト
ルエン等の有機溶剤に溶解させることもでき、したがつ
て被覆用材料、フィルム材料として使用することもでき
る。分子中のフェニル基には常套の方法によつてスルホ
ン基、アミノ基等の置換基を導入することができ、各種
誘導体の合成が可能である他、そのスルホン化物の可撓
性がよいため従来不可能であつた耐熱性イオン交換膜と
して用いることができる。本発明共重合体はTFEとT
FS各単量体を混合・し公知のラジカル重合開始源を用
いて製造することができる。
If the intrinsic viscosity is lower than this, the copolymer will have a low molecular weight and poor shape retention, and the molded product will be brittle and impractical. The TFE-TFS copolymer of the present invention has a content ratio of TFE. If TF is high, the crystallinity is relatively high, and conversely
When the S content is high, the crystallinity decreases, resulting in an amorphous polymer. A particularly remarkable property of this polymer is that its second-order transition temperature (Tg) becomes very high when the TFS content is relatively high. For example, as shown in Example 4, TFS
The secondary transition point of the copolymer with a content of 90.7 mol% is 180
℃, which is at the highest level compared to known polymers. This copolymer also has a thermal decomposition temperature of 350 to 450°C.
Therefore, it has excellent moldability. Furthermore, this copolymer is thermoplastic in nature;
Unlike the homopolymer E, it can be molded by any method such as extrusion, injection, compression, etc. by heating and melting. Furthermore, it can be dissolved in organic solvents such as acetone, methyl ethyl ketone, chloroform, benzene, toluene, etc., and therefore can be used as a coating material or film material. Substituents such as sulfone groups and amino groups can be introduced into the phenyl group in the molecule by conventional methods, making it possible to synthesize various derivatives. It can be used as a heat-resistant ion exchange membrane, which was previously impossible. The copolymer of the present invention is TFE and T
FS can be produced by mixing each monomer and using a known radical polymerization initiation source.

ラジカル重合開始源とは無機または有機の過酸化物を用
いたレドクス重合方法電離放射線を用いる方法等をさす
。重合は水を媒体とした懸濁重合または乳化重合によつ
て行えばよい。重合温度はO〜80℃、圧力5〜300
k91cItの範囲が適当である。実施例1 内容積100m1のステンレス製オートクレーブにTF
′Sl6yl(NH4)2S2080.1g、NaHS
O3O.O5ダ、Cl2H25NH2・HCll.45
fおよび水50yを仕込む。
The radical polymerization initiation source refers to redox polymerization methods using inorganic or organic peroxides, methods using ionizing radiation, and the like. Polymerization may be carried out by suspension polymerization or emulsion polymerization using water as a medium. Polymerization temperature is O~80℃, pressure 5~300℃
A range of k91cIt is appropriate. Example 1 TF in a stainless steel autoclave with an internal volume of 100 m1
'Sl6yl(NH4)2S2080.1g, NaHS
O3O. O5 da, Cl2H25NH2・HCll. 45
Add f and 50y of water.

次いでオートクレーブを密閉し、ドライアイスで冷却し
た後、真空にし、TFEll.5yを加える。内部温度
を40℃に調節し、2碕間振盪する。反応生成物にメタ
ノールを加え生成重合体を凝析させる。凝析物をクロロ
ホルムに溶かし、これをメタノールに注ぎ析出精製粉末
状重合体2.2fを得る。この精製重合体の物性を表−
1に示す。元素分析値から生成重合体のモル比はTFS
:′IFE=90.7:9.3であることがわかる。こ
の共重合体をアセトンに溶かし、ガラス板上に流延しア
セトンを蒸発させると透明な堅いフィルムが得られる。
実施例2 内容積2eのステンレス製オートクレーブに、TF′S
l6fl..FeSO4・7H202.4y1アスコル
ビン酸12y1ラウリル硫酸ナトリウム10yおよび水
500yを仕込む。
The autoclave was then sealed, cooled with dry ice, evacuated, and TFEl. Add 5y. Adjust the internal temperature to 40°C and shake for 2 minutes. Methanol is added to the reaction product to coagulate the resulting polymer. The precipitate was dissolved in chloroform and poured into methanol to obtain a precipitated purified powdery polymer 2.2f. The physical properties of this purified polymer are shown below.
Shown in 1. From the elemental analysis values, the molar ratio of the produced polymer is TFS
:'IFE=90.7:9.3. This copolymer is dissolved in acetone, cast on a glass plate, and the acetone is evaporated to yield a transparent, rigid film.
Example 2 TF'S was placed in a stainless steel autoclave with an internal volume of 2e.
l6fl. .. FeSO4.7H202.4y1 ascorbic acid 12y1 sodium lauryl sulfate 10y and water 500y are charged.

オートクレーブを密閉し、TFE25Oyを加える。内
部温度をO〜5℃に調節し攪拌しながら過酸化水素水(
3%)を定量ポンプを用い24時間で50m1添加する
。オートクレーブから重合液を取り出し、実施例1と同
様にして共重合物を精製し、粉末状共重合物3qを得た
。この共重合体の元素分析値はF:46.1重量%、C
:51.鍾量%、H:2.25重量%であつた。これか
ら計算した共重合体の組成はTFS:TFE=64:3
6モル比である。また極限粘度〔η〕は0.15d11
y(35℃、MEK中)であつた。この共重合体は実施
例1の共重合体と同様アセトン溶液から透明フィルムを
得ることができる。実施例3 TFS16yおよびTFE8OOyを用い反応時間を4
8時間とする以外、実施例2と同様にして共重合体を行
つた。
Seal the autoclave and add 25 Oy of TFE. Adjust the internal temperature to 0~5℃ and add hydrogen peroxide solution (
Add 50 ml of 3%) over 24 hours using a metering pump. The polymerization liquid was taken out from the autoclave, and the copolymer was purified in the same manner as in Example 1 to obtain powdered copolymer 3q. The elemental analysis values of this copolymer are F: 46.1% by weight, C
:51. The weight percentage, H: was 2.25% by weight. The composition of the copolymer calculated from this is TFS:TFE=64:3
The molar ratio is 6. Also, the limiting viscosity [η] is 0.15d11
y (35°C, in MEK). Similar to the copolymer of Example 1, a transparent film can be obtained from this copolymer from an acetone solution. Example 3 Reaction time was 4 using TFS16y and TFE8OOy.
Copolymerization was carried out in the same manner as in Example 2 except that the heating time was 8 hours.

Claims (1)

【特許請求の範囲】 1 式:(CF_2CF_2)および 式:▲数式、化学式、表等があります▼ で示される繰り返し単位を、それぞれ5〜95モル%お
よび95〜5モル%の割合で含有し、メチルエチルケト
ン溶液として35℃で測定した極限粘度が少なくとも約
0.1dl/gであることを特徴とする共重合体。 2 テトラフルオロエチレンとα・β・β−トルフルオ
ロスチレンとをラジカル重合開始源を用いて共重合する
ことを特徴とする、式:(CF_2CF_2)および 式:▲数式、化学式、表等があります▼ で示される繰り返し単位を、それぞれ5〜95モル%お
よび95〜5モル%の割合で割有し、メチルエチルケト
ン溶液として35℃で測定した極限粘度が少なくとも約
0.1dl/gである共重合体の製造方法。
[Claims] 1 Contains repeating units represented by formula: (CF_2CF_2) and formula: ▲Mathematical formula, chemical formula, table, etc.▼ in proportions of 5 to 95 mol% and 95 to 5 mol%, respectively, A copolymer having an intrinsic viscosity of at least about 0.1 dl/g, measured as a solution in methyl ethyl ketone at 35°C. 2 Formula: (CF_2CF_2) and formula: ▲Mathematical formula, chemical formula, table, etc., which are characterized by copolymerizing tetrafluoroethylene and α, β, β-trifluorostyrene using a radical polymerization initiation source. A copolymer containing repeating units represented by 5 to 95 mol% and 95 to 5 mol%, respectively, and having an intrinsic viscosity of at least about 0.1 dl/g as measured as a methyl ethyl ketone solution at 35°C. Production method.
JP10197576A 1976-08-25 1976-08-25 Fluorine-containing copolymer and method for producing the same Expired JPS6046123B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP10197576A JPS6046123B2 (en) 1976-08-25 1976-08-25 Fluorine-containing copolymer and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP10197576A JPS6046123B2 (en) 1976-08-25 1976-08-25 Fluorine-containing copolymer and method for producing the same

Publications (2)

Publication Number Publication Date
JPS5326884A JPS5326884A (en) 1978-03-13
JPS6046123B2 true JPS6046123B2 (en) 1985-10-14

Family

ID=14314854

Family Applications (1)

Application Number Title Priority Date Filing Date
JP10197576A Expired JPS6046123B2 (en) 1976-08-25 1976-08-25 Fluorine-containing copolymer and method for producing the same

Country Status (1)

Country Link
JP (1) JPS6046123B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020071780A1 (en) * 2018-10-05 2020-04-09 제이비엠 주식회사 Multi-purpose mini fan

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5602185A (en) * 1993-09-21 1997-02-11 Ballard Power Systems Inc. Substituted trifluorostyrene compositions
US5422411A (en) * 1993-09-21 1995-06-06 Ballard Power Systems Inc. Trifluorostyrene and substituted trifluorostyrene copolymeric compositions and ion-exchange membranes formed therefrom
US5773480A (en) * 1993-09-21 1998-06-30 Ballard Power Systems Inc. Trifluorostyrene and substituted trifluorostyrene copolymeric compositions and ion-exchange membranes formed therefrom
US5834523A (en) 1993-09-21 1998-11-10 Ballard Power Systems, Inc. Substituted α,β,β-trifluorostyrene-based composite membranes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020071780A1 (en) * 2018-10-05 2020-04-09 제이비엠 주식회사 Multi-purpose mini fan

Also Published As

Publication number Publication date
JPS5326884A (en) 1978-03-13

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