JP2502100B2 - Fluorine-containing compound having epoxy group and vinyl group - Google Patents
Fluorine-containing compound having epoxy group and vinyl groupInfo
- Publication number
- JP2502100B2 JP2502100B2 JP20650887A JP20650887A JP2502100B2 JP 2502100 B2 JP2502100 B2 JP 2502100B2 JP 20650887 A JP20650887 A JP 20650887A JP 20650887 A JP20650887 A JP 20650887A JP 2502100 B2 JP2502100 B2 JP 2502100B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- containing compound
- epoxy group
- group
- mol
- 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
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- Epoxy Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、エポキシ基及びビニル基を有する新規な含
フッ素化合物に関するものである。TECHNICAL FIELD The present invention relates to a novel fluorine-containing compound having an epoxy group and a vinyl group.
［従来の技術］ 従来、エポキシ基を有する（メタ）アクリレート例え
ば、グリシジル（メタ）アクリレート等は知られている
が、フッ素原子を含んでいるエポキシ基含有（メタ）ア
クリレートは今だ知られていない。[Prior Art] Conventionally, (meth) acrylates having an epoxy group, such as glycidyl (meth) acrylate, are known, but epoxy group-containing (meth) acrylates containing a fluorine atom are not yet known. .
［発明の解決しようとする問題点］ 本発明は従来知られていなかったエポキシ基及びビニ
ル基を有する含フッ素化合物を新規に提供することを目
的とするものである。[Problems to be Solved by the Invention] It is an object of the present invention to newly provide a fluorine-containing compound having an epoxy group and a vinyl group, which has not hitherto been known.
［問題点を解決するための手段］ 本発明は一般式（Ｉ） で示されるエポキシ基及びビニル基を有する含フッ素化
合物を提供するものである。[Means for Solving the Problems] The present invention has the general formula (I) The present invention provides a fluorine-containing compound having an epoxy group and a vinyl group represented by
本発明の含フッ素化合物は、撥水撥油剤やフッ素樹脂
の原料モノマー等として有用であり、例えば次のように
して合成することができる。INDUSTRIAL APPLICABILITY The fluorine-containing compound of the present invention is useful as a water- and oil-repellent agent and a raw material monomer for a fluororesin, and can be synthesized, for example, as follows.
I(CF2)aI→ICH2CH2(CF2)aI→HOCH2CH2(CF2)aI （式中ａは１〜10の整数） 即ちα，ω−ジヨードパーフルオロアルカン（１）
を、ラジカル開始剤存在下、エチレンと付加反応させ
（２）を得、クロルスルホン酸を用い加水分解して
（３）とする。（３）をラジカル開始剤存在下、アリル
アルコールに付加させた後、水酸化アルカリの如きアル
カリにより脱ヨウ化水素しエポキシ基含有含フッ素アル
コール（４）を得る。さらに（メタ）アクリル酸クロラ
イドと反応させると目的とする含フッ素化合物（５）が
得られる。I (CF 2 ) a I → ICH 2 CH 2 (CF 2 ) a I → HOCH 2 CH 2 (CF 2 ) a I (In the formula, a is an integer of 1 to 10) That is, α, ω-diiodoperfluoroalkane (1)
Is subjected to an addition reaction with ethylene in the presence of a radical initiator to obtain (2), which is hydrolyzed with chlorosulfonic acid to give (3). (3) is added to allyl alcohol in the presence of a radical initiator, and then deiodinated with an alkali such as alkali hydroxide to obtain an epoxy group-containing fluorine-containing alcohol (4). Further, by reacting with (meth) acrylic acid chloride, the target fluorinated compound (5) is obtained.
また別の方法として次のようにして得ることもでき
る。Alternatively, it can be obtained as follows.
（式中、ａは１〜10の整数） 即ち、α、ω−ジヨードパーフルオロアルカン（１）
をラジカル開始剤存在下、エチレンと付加反応させ
（６）を得、クロルスルホン酸を用いて加水分解して
（７）とする。（７）をエピハロヒドリンと反応させ、
対応するハロヒドリンを生成させ次いで水酸化アルカリ
の如きアルカリにより脱ハロゲン化水素反応でグリシジ
ルエーテル（８）を得、さらに（メタ）アクリル酸クロ
ライドと反応させると目的とする含フッ素化合物が得ら
れる。 (In the formula, a is an integer of 1 to 10) That is, α, ω-diiodoperfluoroalkane (1)
Is reacted with ethylene in the presence of a radical initiator to obtain (6), which is hydrolyzed with chlorosulfonic acid to give (7). Reacting (7) with epihalohydrin,
The corresponding halohydrin is formed, then dehydrohalogenation reaction is carried out with an alkali such as alkali hydroxide to obtain glycidyl ether (8), and further reacted with (meth) acrylic acid chloride to obtain the desired fluorine-containing compound.
α、ω−ジヨードパーフルオロアルカン（１）とエチ
レンとの付加反応は、過酸化物；アゾ化合物等のラジカ
ル開始剤存在下、およそ20〜150℃で実施することがで
き、前記化合物（１）１モルに対し１モルのエチレンを
反応させることにより前述の化合物（２）を得ることが
でき、２モルのエチレンを反応させることにより、前述
の化合物（６）を得ることができる。The addition reaction of α, ω-diiodoperfluoroalkane (1) with ethylene can be carried out at about 20 to 150 ° C. in the presence of a radical initiator such as a peroxide or an azo compound. ) The above-mentioned compound (2) can be obtained by reacting 1 mol of ethylene with respect to 1 mol, and the above-mentioned compound (6) can be obtained by reacting 2 mol of ethylene.
化合物（２）及び（６）の加水分解反応はクロルスル
ホン酸、発煙硫酸等の酸を用いておよそ０〜100℃で実
施すればよく、対応する前述の化合物（３）及び（７）
を得ることができる。The hydrolysis reaction of the compounds (2) and (6) may be carried out using an acid such as chlorosulfonic acid and fuming sulfuric acid at about 0 to 100 ° C., and the corresponding compounds (3) and (7)
Can be obtained.
化合物（３）とアリルアルコールを過酸化物、アゾ化
合物等のラジカル開始剤存在下、およそ20〜150℃で付
加反応させた後、水酸化カリウム、水酸化ナトリウム等
のアルカリにより、およそ０〜120℃、0.1〜３時間で脱
ヨウ化水素し、エポキシ含有含フッ素アルコール（４）
を得ることができる。一方、化合物（７）はエピクロル
ヒドリン等のエピハロヒドリンとおよそ30〜150℃で反
応させ、対応するハロヒドリンを生成させた後、水酸化
カリウム、水酸化ナトリウム等のアルカリにより脱ハロ
ゲン化水素反応を行ない、グリシジルエーテル（８）を
得ることができる。Compound (3) and allyl alcohol are subjected to an addition reaction in the presence of a radical initiator such as a peroxide or an azo compound at about 20 to 150 ° C., and then an alkali reaction such as potassium hydroxide or sodium hydroxide is performed at about 0 to 120 ° C. Dehydroiodinated in 0.1 to 3 hours at ℃, epoxy-containing fluorine-containing alcohol (4)
Can be obtained. On the other hand, the compound (7) is reacted with epihalohydrin such as epichlorohydrin at about 30 to 150 ° C. to produce the corresponding halohydrin, and then dehydrohalogenation reaction is carried out with an alkali such as potassium hydroxide or sodium hydroxide to give glycidyl. Ether (8) can be obtained.
化合物（４）や（８）は、（メタ）アクリル酸クロラ
イド等の（メタ）アクリル酸ハライドとおよそ−20〜10
0℃、0.1〜３時間反応させ、目的とする本発明の含フッ
素化合物を得ることができる。反応は無溶媒にて実施可
能であるが必要に応じて溶媒を使用することができる。
溶媒としては、（メタ）アクリル酸ハライドと反応しな
いものであれば特に制限はないが、例えば酢酸エチル、
酢酸ブチル、アセトン、メチルエチルケトン、テトラヒ
ドロフラン、ベンゾトリフロリド等の非プロトン系溶媒
を用いることが好ましい。また（メタ）アクリル酸ハラ
イドと反応しないアミンを共存させて反応してもよい。Compounds (4) and (8) are about −20 to 10 with (meth) acrylic acid halides such as (meth) acrylic acid chloride.
The desired fluorine-containing compound of the present invention can be obtained by reacting at 0 ° C for 0.1 to 3 hours. The reaction can be carried out without a solvent, but a solvent can be used if necessary.
The solvent is not particularly limited as long as it does not react with the (meth) acrylic acid halide, for example, ethyl acetate,
It is preferable to use an aprotic solvent such as butyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran, or benzotrifluoride. Further, an amine that does not react with the (meth) acrylic acid halide may coexist and react.
［実施例］ 実施例１ ICH2CH2(CF2)4I（２）164g（0.32mol）にクロルスル
ホン酸106g（0.91mol）を50℃でゆっくり滴下し、２時
間熟成する。H2Oをゆっくり加えた後Na2SO3水溶液、イ
ソプロピルアルコールを加え30分間80℃で加水分解す
る。分液によりHOCH2CH2(CF2)4I（３）を得た。収量111
g（収率93％）。Example 1 Example 1 164 g (0.32 mol) of ICH 2 CH 2 (CF 2 ) 4 I (2) was slowly added dropwise with 106 g (0.91 mol) of chlorosulfonic acid at 50 ° C. and aged for 2 hours. After slowly adding H 2 O, a Na 2 SO 3 aqueous solution and isopropyl alcohol are added and hydrolysis is performed at 80 ° C. for 30 minutes. HOCH 2 CH 2 (CF 2 ) 4 I (3) was obtained by liquid separation. Yield 111
g (93% yield).
上記ヨウ化物（３）100g（0.27mol）に、アリルアル
コール18.7g（0.32mol），α，α′−アゾビス（イソブ
チロニトリル）1.3gを加え80℃で８時間反応させる。減
圧下、未反応物及び過剰のアリルアルコールを留去した
後、30％水酸化カリウム水溶液50g,アセトン50mlを加え
30分間反応させる。エーテル抽出後蒸留により を得た。収量66g（収率81％）沸点98℃/0.2mmHg。To 100 g (0.27 mol) of the iodide (3), 18.7 g (0.32 mol) of allyl alcohol and 1.3 g of α, α'-azobis (isobutyronitrile) are added and reacted at 80 ° C for 8 hours. After distilling off unreacted substances and excess allyl alcohol under reduced pressure, 50% 30% aqueous potassium hydroxide solution and 50 ml acetone were added.
Incubate for 30 minutes. After extraction with ether and distillation I got Yield 66g (81% yield) Boiling point 98 ° C / 0.2mmHg.
上記アルコール（４）64g（0.21mol）、トリエチルア
ミン21g（0.21mol）の酢酸エチル溶液にメタクリル酸ク
ロライド22g（0.21mol）を０℃で滴下する。室温で２時
間熟成後、加水分解，エーテル抽出し、無水Na2SO4で乾
燥した後、エーテルを留去し目的物 を得た。収量64g（収率82％） 1HNMR（δppm,acetone−ｄ6）1.8（3H,CH2＝Ｃ（C
H3 ））， 4.4（2H,OCH2 CH2）,5.5（1H,CH2 ＝Ｃ（CH3））,6.0（1
H,CH2 ＝Ｃ（CH3））；19F NMR（δppm,acetone−ｄ6）
−112（2F,−CF2CF2CF2 CF2−），−113（2F,−CF2CF2CF
2 CF2−），−124（4F,−CF2 CF2CF2CF2 −）,MS（m/e）35
4（1.1％,M+−16）,86（12％）,69（100％）,41（69
％）。To the ethyl acetate solution of 64 g (0.21 mol) of the alcohol (4) and 21 g (0.21 mol) of triethylamine, 22 g (0.21 mol) of methacrylic acid chloride was added dropwise at 0 ° C. After aging at room temperature for 2 hours, hydrolysis, extraction with ether, drying over anhydrous Na 2 SO 4 and evaporation of ether to obtain the desired product. I got Yield 64 g (yield 82%) 1 HNMR (δ ppm , acetone-d 6 ) 1.8 (3H, CH 2 ═C ( C
H 3 )), 4.4 (2H, OC H 2 CH 2 ), 5.5 (1H, C H 2 = C (CH 3 )), 6.0 (1
H, C H 2 = C (CH 3 )); 19 F NMR (δ ppm , acetone-d 6 ).
−112 (2F, −CF 2 C F 2 CF 2 CF 2 −), −113 (2F, −CF 2 C F 2 CF
2 CF 2 −), −124 (4F, −C F 2 CF 2 CF 2 C F 2 −), MS (m / e) 35
4 (1.1%, M + −16), 86 (12%), 69 (100%), 41 (69
%).
実施例２ HOCH2CH2CF2CF2CF2CF2CH2CH2OH33.7g（0.116mol）と3
0％水酸化ナトリウム水溶液15.5gを100mlの３口フラス
コに入れ90℃にした。３時間加熱後、110℃に加熱し、
減圧により２時間脱水し、固体を得た。アセトン40mlを
加え固体を溶かした後、室温でエピクロルヒドリン10.7
gを加え、50℃で４時間熟成した。冷却後、水40mlを加
え、エーテル抽出し、無水硫酸ナトリウムで一晩乾燥後
濃縮し、 （収率88％）を得た。1HNMR（δppm,acetone−ｄ6）1.9
0〜2.60（6H,HOCH2 CH2 CF2， 19FNMR（δppm）−113.8（4F,CF2 CF2CF2 CF2 ），−124.0
（4F,CF2 CF2CF2 CF2）。Example 2 HOCH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 OH 33.7 g (0.116 mol) and 3
15.5 g of 0% sodium hydroxide aqueous solution was placed in a 100 ml three-necked flask and the temperature was raised to 90 ° C. After heating for 3 hours, heat to 110 ℃,
It was dehydrated for 2 hours under reduced pressure to obtain a solid. After adding 40 ml of acetone to dissolve the solid, at room temperature epichlorohydrin 10.7
g was added and the mixture was aged at 50 ° C. for 4 hours. After cooling, 40 ml of water was added, extracted with ether, dried over anhydrous sodium sulfate overnight and concentrated, (88% yield) was obtained. 1 HNMR (δ ppm , acetone-d 6 ) 1.9
0 to 2.60 (6H, HOCH 2 CH 2 CF 2 , 19 FNMR (δ ppm ) -113.8 (4F, CF 2 CF 2 CF 2 CF 2 ), -124.0
(4F, CF 2 CF 2 CF 2 CF 2 ).
上記エポキシ基含有アルコール8.65g（25mmol）と、
トリエチルアミン3.03gと酢酸エチル30mlを100mlの３口
フラスコに入れ０℃でメタクリル酸クロライド3.13gを
滴下した。室温で２時間成熟後、水40mlを加え、エーテ
ル抽出した。無水硫酸ナトリウムで一晩乾燥後濃縮し、 8.14g（収率79％）を得た。1HNMR（δppm,acetone−
ｄ6）,1.90（3H,CH3）,2.00〜2.90（6H, ）， 3.60〜4.10（4H, ）,4.45（2H, 5.62（1H,CH2 ＝Ｃ）,6.08（1H,CH2 ＝Ｃ），19FNMR（δ
ppm）−113.0（4F,CF2 CF2CF2 CF2 ），−123.1（4F,CF2 CF
2CF2 CF2）。With 8.65 g (25 mmol) of the above epoxy group-containing alcohol,
3.03 g of triethylamine and 30 ml of ethyl acetate were placed in a 100 ml three-necked flask, and 3.13 g of methacrylic acid chloride was added dropwise at 0 ° C. After maturation at room temperature for 2 hours, 40 ml of water was added and the mixture was extracted with ether. Concentrate after drying over anhydrous sodium sulfate overnight. 8.14 g (yield 79%) was obtained. 1 HNMR (δ ppm , acetone−
d 6 ), 1.90 (3H, CH 3 ), 2.00 to 2.90 (6H, ), 3.60 ~ 4.10 (4H, ), 4.45 (2H, 5.62 (1H, CH 2 = C), 6.08 (1H, CH 2 = C), 19 FNMR (δ
ppm ) −113.0 (4F, CF 2 CF 2 CF 2 CF 2 ), −123.1 (4F, CF 2 CF
2 CF 2 CF 2 ).
本発明の含フッ素化合物は、性質の異なった重合可能
な部位を２ケ所すなわち、ビニル基とエポキシ基を有し
ている上にパーフルオロアルキレン基を有していること
から他の含フッ素化合物との相溶性が著しく向上し、高
度に架橋した含フッ素ポリマーや含フッ素グラフトポリ
マー等を合成する際に極めて有効であり、例えば、含フ
ッ素撥水撥油剤、フッ素樹脂、フッ素ゴムあるいは各種
含フッ素表面改質剤の原料モノマーとして有用である。Since the fluorine-containing compound of the present invention has two polymerizable sites having different properties, that is, it has a vinyl group and an epoxy group and further has a perfluoroalkylene group, it is different from other fluorine-containing compounds. The compatibility is significantly improved, and it is extremely effective in synthesizing highly crosslinked fluoropolymers and graft polymers, such as fluorine-containing water and oil repellents, fluororesins, fluororubbers and various fluorine-containing surfaces. It is useful as a raw material monomer for the modifier.
Claims (1)
ニル基を有する含フッ素化合物。 1. A fluorine-containing compound having an epoxy group and a vinyl group represented by formula (I).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20650887A JP2502100B2 (en) | 1987-08-21 | 1987-08-21 | Fluorine-containing compound having epoxy group and vinyl group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20650887A JP2502100B2 (en) | 1987-08-21 | 1987-08-21 | Fluorine-containing compound having epoxy group and vinyl group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6450875A JPS6450875A (en) | 1989-02-27 |
| JP2502100B2 true JP2502100B2 (en) | 1996-05-29 |
Family
ID=16524530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20650887A Expired - Lifetime JP2502100B2 (en) | 1987-08-21 | 1987-08-21 | Fluorine-containing compound having epoxy group and vinyl group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2502100B2 (en) |
-
1987
- 1987-08-21 JP JP20650887A patent/JP2502100B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6450875A (en) | 1989-02-27 |
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