JPH066543B2 - Fluorinated diallyl ether - Google Patents
Fluorinated diallyl etherInfo
- Publication number
- JPH066543B2 JPH066543B2 JP62088358A JP8835887A JPH066543B2 JP H066543 B2 JPH066543 B2 JP H066543B2 JP 62088358 A JP62088358 A JP 62088358A JP 8835887 A JP8835887 A JP 8835887A JP H066543 B2 JPH066543 B2 JP H066543B2
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- Prior art keywords
- diallyl ether
- formula
- reaction
- fluorinated
- fraction
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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、新規なフッ素化ジアリルエーテルに関する。TECHNICAL FIELD The present invention relates to a novel fluorinated diallyl ether.
従来、両末端に官能基を持つヘキサフロプロピレンオキ
サイド重合体、すなわち式： 〔ここで、ｍ及びｎは０〜２０の整数で、ｍ＋２＝０〜
２０である〕 で表わされる化合物としては、例えば、Ｒが-COOX，-CF
2X（Ｘは、アルキル基またはアリール基）、 -COOH，-CH2OHなどであるものが報告されている（特開
昭60-156726）。しかし、両末満の官能基がアリル基で
あるものは知られていない。Conventionally, a hexafluoropropylene oxide polymer having a functional group at both ends, that is, the formula: [Here, m and n are integers of 0 to 20, and m + 2 = 0 to
20], for example, R is —COOX, —CF
2 X (X is an alkyl group or an aryl group), -COOH, -CH 2 OH and the like have been reported (JP-A-60-156726). However, it is not known that the functional group on both ends is an allyl group.
〔発明の目的〕 本発明の目的は、新規なフッ素化ジアリルエーテルを提
供することにあり、特にシリコーン諸特性を向上させる
ことができる改質用中間原料、ゴムの過酸化物加硫に用
いる架橋剤、ビニル重合用モノマー等として有用なフッ
素化ジアリルエーテルを提供することにある。[Object of the invention] It is an object of the present invention to provide a novel fluorinated diallyl ether, particularly a modifying intermediate material capable of improving various silicone properties, cross-linking used for peroxide vulcanization of rubber. An object of the present invention is to provide a fluorinated diallyl ether useful as an agent, a monomer for vinyl polymerization and the like.
即ち、本発明は、 一般式(I)： 〔式中、ｍ及びｎは、独立に、０〜２の整数であつて、
ｍ＋ｎ＝０、１又は２を満たす。〕 で表わされるフッ素化ジアリルエーテルを提供するもの
である。That is, the present invention has the general formula (I): [In the formula, m and n are each independently an integer of 0 to 2,
m + n = 0, 1 or 2 is satisfied. ] It is what provides the fluorinated diallyl ether represented by these.
本発明の一般式(I)のフッ素化ジアリルエーテルは、例
えば、式(II) 〔式中、ｍ及びｎは一般式(I)と同じ〕 で表わされる両末端酸フルオライド化合物を、アルカリ
金属フッ化物（MF、ただしＭはアルカリ金属）と反応さ
せて、式(III)： 〔ここで、ｍ及びｎは一般式(I)と同じ〕 で表わされるフルオロアルコラートを生成させ、次に該
フルオロアルコラートをハロゲン化アリル（CH2＝CHCH2
X，Ｘはハロゲン原子）と反応させることにより、本発
明の前記一般式(I)のフッ素化ジアリルエーテルが生成
する。The fluorinated diallyl ether of the general formula (I) of the present invention has, for example, the formula (II) [In the formula, m and n are the same as those in the general formula (I)], and an acid fluoride compound having both terminals is reacted with an alkali metal fluoride (MF, where M is an alkali metal) to give a compound represented by the formula (III): [Wherein, m and n are the same as those in the general formula (I)], and then the fluoroalcoholate is converted into an allyl halide (CH 2 ═CHCH 2
By reacting X and X with a halogen atom, the fluorinated diallyl ether of the general formula (I) of the present invention is produced.
この製法において、式(II)の両末端酸フルオライド化合
物とアルカリ金属フッ化物とアルカリ金属フッ化物との
反応は、溶媒として、例えば、テトラエチレングリコー
ルジメチルエーテル、トリエチレングリコールジメチル
エーテル、ジエチレングリコールジメチルエーテル、ジ
オキサン等を用い、実質的に無水の条件下で行なうこと
が必要で、例えば、乾燥窒素雰囲気中で行ない、反応
物、溶媒は十分に乾燥したものを用いる。反応における
両反応成分の濃度は、溶媒１モルに対して両末端酸フル
オライド化合物0.2〜１モル、アルカリ金属フッ化物は
両末端酸フルオライド化合物１モルに対して２〜2.4倍
モル程度が好しく、このときアルカリ金属フッ化物の使
用量は両末端酸フルオライド化合物に対しモル比で２倍
以上、特に2.4倍以上用いることが好ましい。また、０
〜50℃において１〜５時間程度反応させる。通常、アル
カリ金属フッ化物を溶媒に懸濁させておいて、式(II)の
両末端酸フルオライド化合物を、必要ならば溶媒ととも
に、滴下させればよい。この段階で用いられるアルカリ
金属フッ化物としては、例えば、セシウム、ルビジウ
ム、カリウム、ナトリウムのフッ化物があげられる。In this production method, the reaction between the acid fluoride compound having terminals at both ends of the formula (II), the alkali metal fluoride and the alkali metal fluoride is carried out as a solvent, for example, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane and the like. It is necessary to use it under substantially anhydrous conditions. For example, the reaction is carried out in a dry nitrogen atmosphere, and the reaction product and solvent are sufficiently dried. The concentration of both reaction components in the reaction is preferably 0.2 to 1 mol of both terminal acid fluoride compounds with respect to 1 mol of the solvent, and the alkali metal fluoride is preferably about 2 to 2.4 times mol with respect to 1 mol of both terminal acid fluoride compounds, At this time, it is preferable to use the alkali metal fluoride in an amount of 2 times or more, particularly 2.4 times or more, in molar ratio with respect to the acid fluoride compound at both ends. Also, 0
The reaction is carried out at -50 ° C for about 1-5 hours. Usually, the alkali metal fluoride is suspended in the solvent, and the both-end acid fluoride compound of the formula (II) may be added dropwise together with the solvent if necessary. Examples of the alkali metal fluoride used at this stage include cesium, rubidium, potassium, and sodium fluorides.
上記の反応により、反応混合物中に式(III)のフルオロ
アルコラートが生成するが、次段階はこうして得られた
反応混合物に臭化アリル、塩化アリル、ヨウ化アリル等
のハロゲン化アリルを添加すればよい。この反応も実質
的に無水の条件で行なうことが必要で、０〜100℃にお
いて１〜20時間程度反応させる。この結果、一般式(I)
のフッ素化ジアリルエーテルが生成する。ハロゲン化ア
リルの使用量は用いた両末端酸フルオライド化合物の２
〜４倍モル程度でよい。The above reaction produces a fluoroalcoholate of formula (III) in the reaction mixture, but the next step is to add allyl bromide, allyl chloride, allyl iodide or other halogenated allyl halide to the reaction mixture thus obtained. Good. This reaction also needs to be carried out under substantially anhydrous conditions, and the reaction is carried out at 0 to 100 ° C. for about 1 to 20 hours. As a result, the general formula (I)
Fluorinated diallyl ether of is produced. The amount of allyl halide used is 2 for the acid fluoride compound at both ends used.
It may be about 4 times the molar amount.
得られた反応混合物から目的生成物を分離するには、例
えば、反応混合物に過剰のメタノールを添加して末反応
の式(II)で表わされる両末端酸フルオライド化合物の末
端をメチルエステル化した後水洗し、蒸留により式(I)
のフッ素化ジアリルエーテルを得ることができる。To separate the desired product from the obtained reaction mixture, for example, after adding excess methanol to the reaction mixture to methyl esterify the terminals of both terminal acid fluoride compounds represented by formula (II) of the end reaction Formula (I) by washing with water and distillation
The fluorinated diallyl ether can be obtained.
上記の製法に出発原料として用いられる式(II)の両末端
フルオライド化合物は、特公昭53-5360号公報に記載の
方法により製造することができるものである。The both-end fluoride compound of the formula (II) used as a starting material in the above production method can be produced by the method described in JP-B-53-5360.
次に、本発明を実施例により、より詳細に説明する。 Next, the present invention will be described in more detail by way of examples.
実施例１ 特公昭53-5360号公報記載の方法により、下記のように
して両末端酸フルオライド化合物を製造した。Example 1 By the method described in JP-B-53-5360, an acid fluoride compound having both terminal ends was produced as follows.
まず、式： で表わされる化合物の46.5量％のテトラグライム溶液を
調製した。この溶液717ｇをスパイラルトラップを備え
た１のフラスコに仕込み、トラップの温度を−75℃
に、フラスコの温度を−30℃に調節した後、撹拌しなが
らヘキサフルオロプロピレンオキサイド192ｇを仕込
み、約１時間撹拌を続けた。次に、フラスコの内容物を
そのまま減圧蒸留し、３mmHgにて沸点45〜50℃の留分を
集めた。こうして得られた留分は、ガスクロマトグラフ
ィーの分析において、留分をそのまま分析した場合のリ
テンションタイムおよびピーク面積または留分をメタノ
ールと反応させて両末端メチルエステル化した試料を分
析した場合のリテンションタイムおよびピーク面積か
ら、さらに両者を比較することにより、前記式(IV)のア
ルコラート化合物に対するヘキサフルオロプロピレンオ
キサイドの１付加体（28重量％）と２付加体（60重量
％）である下記の式： 〔ここで、ｍ及びｎは、それぞれ０〜２の整数であつ
て、ｍ＋ｎ＝１又は２である〕 で表わされる両末端酸フルオライド化合物を含む混合物
であることがわかった。First, the formula: A 46.5% by weight tetraglyme solution of the compound represented by 717 g of this solution was charged into a flask equipped with a spiral trap, and the temperature of the trap was -75 ° C.
After adjusting the temperature of the flask to −30 ° C., 192 g of hexafluoropropylene oxide was charged with stirring, and stirring was continued for about 1 hour. Next, the contents of the flask were directly distilled under reduced pressure to collect a fraction having a boiling point of 45 to 50 ° C. at 3 mmHg. The fraction thus obtained is the retention time and peak area in the case of analyzing the fraction as it is in the analysis by gas chromatography, or the retention in the case of analyzing the sample in which both ends are methyl esterified by reacting the fraction with methanol. From the time and the peak area, by further comparing the two, the following formulas, which are 1 adduct (28% by weight) and 2 adducts (60% by weight) of hexafluoropropylene oxide with respect to the alcoholate compound of the above formula (IV), are obtained. : [Here, m and n are integers of 0 to 2, respectively, and m + n = 1 or 2] It was found that the mixture contains the acid fluoride compound at both terminals.
次にこの両末端酸フルオライド化合物を含む混合物45・7
ｇ、フッ化セシウム24.1ｇおよびテトラグライム64.0ｇ
を０．５のフラスコに仕込み、約12時間室温で撹拌し
た後、臭化アリル35.0ｇを滴下し、フラスコを70℃に加
温して３時間撹拌を続けた。反応終了後、フラスコの内
容物を水洗、分液して前記の酸フルオライド化合物に対
応するジアリルエーテルを含有する混合物38.0ｇを得
た。この生成混合物を減圧蒸留することにより、沸点95
℃／２mmHgの留分(A)8.1gと沸点110℃／２mmHgの留分
(B)15.8gを得た。Next, a mixture containing both acid fluoride compounds at both ends 45.7
g, cesium fluoride 24.1g and tetraglyme 64.0g
Was charged in a 0.5 flask and stirred at room temperature for about 12 hours, 35.0 g of allyl bromide was added dropwise, the flask was heated to 70 ° C., and stirring was continued for 3 hours. After completion of the reaction, the contents of the flask were washed with water and separated to obtain 38.0 g of a mixture containing the diallyl ether corresponding to the acid fluoride compound. The product mixture was distilled under reduced pressure to give a boiling point of 95
℃ / 2mmHg fraction (A) 8.1g and boiling point 110 ℃ / 2mmHg fraction
(B) 15.8 g was obtained.
下記に示す分析結果から、留分(A)及び(B)はそれぞれ次
の式で示されるフッ素化ジアリルエーテルであることが
わかつた。From the analysis results shown below, it was found that the fractions (A) and (B) were each a fluorinated diallyl ether represented by the following formula.
(1) 留分(A)： 赤外吸収スペクトル：cm-1（図１） 1660（アリル基のＣ＝Ｃ） 質量分析：分子量712 元素分析： Ｃ Ｆ Ｏ Ｈ 計算値（重量％） 28.65 58.71 11.24 1.40 実測値（重量％） 28.42 59.12 10.95 1.51 (2) 留分(B) 〔式中ｍ及びｎは独立に０〜２の整数でありｍ＋ｎ＝２
を満たす。〕 赤外吸収スペクトル：cm-1（図２） 1660（アリル基のＣ＝Ｃ） 質量分析：分子量 878 元素分析： Ｃ Ｆ Ｏ Ｈ 計算値（重量％） 27.33 60.59 10.93 1.14 実測値（重量％） 27.52 60.71 10.68 1.09 実施例２ 実施例１と同様に、特公昭53-5360号公報記載の方法に
より、式 で表わされる両末端酸フルオライド化合物を製造した。(1) Fraction (A): Infrared absorption spectrum: cm -1 (Fig. 1) 1660 (C = C of allyl group) Mass analysis: Molecular weight 712 Elemental analysis: CFOH calculated value (wt%) 28.65 58.71 11.24 1.40 Measured value (wt%) 28.42 59.12 10.95 1.51 (2) Fraction (B) [In the formula, m and n are each independently an integer of 0 to 2, and m + n = 2
Meet ] Infrared absorption spectrum: cm -1 (Fig. 2) 1660 (C = C of allyl group) Mass analysis: Molecular weight 878 Elemental analysis: CFOH calculated value (wt%) 27.33 60.59 10.93 1.14 Measured value (wt%) 27.52 60.71 10.68 1.09 Example 2 As in Example 1, by the method described in JP-B-53-5360, the formula A both-end acid fluoride compound represented by
次に、該酸フルオライド化合物316g、フッ化セシウム35
0gおよびテトラグライム1025gを、２のフラスコに仕
込み、室温で16時間撹拌した後、臭化アリル370gを滴下
し、70℃にて２時間撹拌を続けた。反応終了後、内容物
を濾過して固形分を取り除き、さらに水洗、分液して有
機層609gを分離した。該有機層を減圧蒸留して沸点70℃
／１mmHgの留分を集め、143gを得た。Next, 316 g of the acid fluoride compound and cesium fluoride 35
0 g and 1025 g of tetraglyme were charged into a flask No. 2 and stirred at room temperature for 16 hours, then 370 g of allyl bromide was added dropwise and the stirring was continued at 70 ° C. for 2 hours. After the reaction was completed, the content was filtered to remove the solid content, followed by washing with water and liquid separation to separate 609 g of an organic layer. The organic layer is distilled under reduced pressure to give a boiling point of 70 ° C.
A fraction of 1 mmHg was collected to obtain 143 g.
このようにして得られた留分は、下記に示す分析結果か
ら式： で表わされるフッ素化ジアリルエーテル（純度99％）で
あることがわかつた。The fraction thus obtained has the formula: It was found to be a fluorinated diallyl ether represented by (purity 99%).
赤外吸収スペクトル：cm-1（図３） 1660（アリル基のＣ＝Ｃ） 質量分析：分子量546 元素分析： Ｃ Ｆ Ｏ Ｈ 計算値（重量％） 30.77 55.68 11.72 1.83 実測値（重量％） 31.14 55.11 11.74 2.01 〔発明の効果〕 本発明のフッ素化ジアリルエーテルは、ケイ素に結合し
た水素 を含有するシラン又はシロキサンとの付加反応を適用で
きるので、フルオロシリコーン合成の中間原料として有
用であり、シリコーンの耐熱性、耐薬品性、耐候性、表
面特性（撥水撥油性、潤滑性、防汚性）、気体透過性等
の特性向上、屈折率の低減などを図ることができる。ま
た、過酸化物などのラジカル開始剤と組合わせて例えば
ゴム加硫の架橋助剤として、またビニル重合用モノマー
として有用である。Infrared absorption spectrum: cm -1 (Fig. 3) 1660 (C = C of allyl group) Mass analysis: molecular weight 546 Elemental analysis: CFOH calculated value (wt%) 30.77 55.68 11.72 1.83 Measured value (wt%) 31.14 55.11 11.74 2.01 [Effect of the invention] The fluorinated diallyl ether of the present invention is hydrogen bonded to silicon. Since it is applicable to addition reaction with silane or siloxane containing, it is useful as an intermediate raw material for fluorosilicone synthesis, and has heat resistance, chemical resistance, weather resistance, and surface properties (water and oil repellency, lubricity, protection, etc.) of silicone. It is possible to improve characteristics such as dirtiness) and gas permeability, and reduce the refractive index. Further, it is useful in combination with a radical initiator such as peroxide, for example, as a crosslinking aid for rubber vulcanization and as a monomer for vinyl polymerization.
図１は実施例１で得られた留分(A)のフッ素化ジアリル
エーテルの赤外吸収スペクトルを示し、図２は同じく留
分(B)のフッ素化ジアリルエーテルの赤外吸収スペクト
ルを示し、図３は実施例２で得られたフッ素化ジアリル
エーテルの赤外吸収スペクトルを示す。1 shows the infrared absorption spectrum of the fluorinated diallyl ether of the fraction (A) obtained in Example 1, FIG. 2 shows the infrared absorption spectrum of the fluorinated diallyl ether of the fraction (B), FIG. 3 shows an infrared absorption spectrum of the fluorinated diallyl ether obtained in Example 2.
フロントページの続き (72)発明者 山本 靖 群馬県安中市磯部２丁目13番１号 信越化 学工業株式会社シリコーン電子材料技術研 究所内 (72)発明者 鷹合 俊雄 群馬県安中市磯部２丁目13番１号 信越化 学工業株式会社シリコーン電子材料技術研 究所内 (56)参考文献 特開 昭60−156726（ＪＰ，Ａ) 特開 昭55−17336（ＪＰ，Ａ)Front page continuation (72) Inventor Yasushi Yamamoto 2-13-1, Isobe, Annaka City, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Toshio Takaai 2 Isobe, Annaka City, Gunma Prefecture 13-1 No. 13 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) References JP-A-60-156726 (JP, A) JP-A-55-17336 (JP, A)
Claims (1)
ｍ＋ｎ＝０、１又は２を満たす。〕 で表わされるフッ素化ジアリルエーテル。1. A general formula (I) [In the formula, m and n are each independently an integer of 0 to 2,
m + n = 0, 1 or 2 is satisfied. ] A fluorinated diallyl ether represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62088358A JPH066543B2 (en) | 1987-04-10 | 1987-04-10 | Fluorinated diallyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62088358A JPH066543B2 (en) | 1987-04-10 | 1987-04-10 | Fluorinated diallyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63253045A JPS63253045A (en) | 1988-10-20 |
| JPH066543B2 true JPH066543B2 (en) | 1994-01-26 |
Family
ID=13940588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62088358A Expired - Lifetime JPH066543B2 (en) | 1987-04-10 | 1987-04-10 | Fluorinated diallyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH066543B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0822828B2 (en) * | 1987-12-28 | 1996-03-06 | 株式会社トクヤマ | Fluorine-containing alkenyl ether compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5517336A (en) * | 1978-07-25 | 1980-02-06 | Asahi Glass Co Ltd | New fluoroolefin compound and its preparation |
| US4647413A (en) * | 1983-12-27 | 1987-03-03 | Minnesota Mining And Manufacturing Company | Perfluoropolyether oligomers and polymers |
-
1987
- 1987-04-10 JP JP62088358A patent/JPH066543B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63253045A (en) | 1988-10-20 |
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