JP2532095B2 - Fluorine-containing spiro orthoester - Google Patents
Fluorine-containing spiro orthoesterInfo
- Publication number
- JP2532095B2 JP2532095B2 JP62128416A JP12841687A JP2532095B2 JP 2532095 B2 JP2532095 B2 JP 2532095B2 JP 62128416 A JP62128416 A JP 62128416A JP 12841687 A JP12841687 A JP 12841687A JP 2532095 B2 JP2532095 B2 JP 2532095B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- spiro orthoester
- containing spiro
- mmol
- compound
- 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
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、新規含フッ素スピロオルトエステルに関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a novel fluorine-containing spiro orthoester.
［従来の技術］ 従来から、分子構造に、スピロオルトエステル構造を
含有する化合物の重合体は、重合時に収縮性を示さない
という特異な特徴を有していることは知られている。一
方、分子構造にフッ素を含有する化合物もその生理活
性、低表面エネルギー性、低屈折率、熱的、化学的安定
性等特異な物性を発現することが知られている。[Prior Art] It has been conventionally known that a polymer of a compound containing a spiro orthoester structure in its molecular structure has a peculiar feature that it does not exhibit shrinkage during polymerization. On the other hand, it is known that a compound containing fluorine in its molecular structure also exhibits unique physical properties such as physiological activity, low surface energy, low refractive index, thermal and chemical stability.
［発明が解決しようとする問題点］ 本発明は、分子内に重合性部位としてスピロオルトエ
ステル基及び機能性部位としてポリフルオロアルキル基
を併せ持つ、モノマーとしても有用な新規化合物を提供
することを目的とするものである。すなわち、重合時非
収縮性と、生理活性、低表面エネルギー性、低屈折性
率、熱・化学的安定性を有する材料は、医薬、撥水撥油
剤、光学材料等の広範な用途に有用である。[Problems to be Solved by the Invention] An object of the present invention is to provide a novel compound useful as a monomer, which has a spiro orthoester group as a polymerizable site and a polyfluoroalkyl group as a functional site in the molecule. It is what That is, a material having non-contraction property during polymerization, physiological activity, low surface energy property, low refractive index, and thermal / chemical stability is useful for a wide range of applications such as medicines, water / oil repellents and optical materials. is there.
［問題点を解決するための手段］ 本発明の新規な含フッ素スピロオルトエステルは、 下記一般式（Ｉ）で表わされる。[Means for Solving Problems] The novel fluorine-containing spiro orthoester of the present invention is represented by the following general formula (I).
式中、RfはC8F17−を示す。 In the formula, Rf represents C 8 F 17 −.
本発明の新規化合物は、例えば、２−パーフルオロオ
クチルエタノールとエピクロロヒドリンを水酸化ナトリ
ウムの如き塩基存在下、通常の反応条件で反応させるこ
とにより、グリシジル基を有する化合物を生成せしめ、 これを触媒量の三フッ化ホウ素エーテル錯体の如きカ
チオン触媒存在下、塩化メチレン、クロロホルム、四塩
化炭素、1,1,2−トリクロロトリフルオロエタン等のハ
ロゲン化炭化水素を代表例とする不活性溶媒中で、例え
ばε−カプロラクトンと反応させる方法により生成可能
である。The novel compound of the present invention, for example, by reacting 2-perfluorooctylethanol and epichlorohydrin in the presence of a base such as sodium hydroxide under normal reaction conditions to form a compound having a glycidyl group, This is a typical example of a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and 1,1,2-trichlorotrifluoroethane in the presence of a catalytic amount of a cationic catalyst such as a boron trifluoride ether complex. It can be produced by a method of reacting with ε-caprolactone in a solvent.
式（III）に示す反応は、含フッ素エポキシドに対し
て、0.1〜10mol％の触媒量で進行するが、重合生成物の
生成を抑える目的で通常1.0〜8.0mol％の量が使用され
る。反応温度は−20℃〜−50℃、好ましくは０℃〜15℃
である。あまりに温度が低いと、反応は進行せず、高す
ぎると副反応を引き起すため好ましくない。 The reaction represented by the formula (III) proceeds with a catalyst amount of 0.1 to 10 mol% with respect to the fluorinated epoxide, but an amount of 1.0 to 8.0 mol% is usually used for the purpose of suppressing the production of polymerization products. Reaction temperature is -20 ° C to -50 ° C, preferably 0 ° C to 15 ° C
Is. If the temperature is too low, the reaction will not proceed, and if it is too high, side reactions will occur, which is not preferable.
カチオン触媒としては、五塩化アンチモン、五フッ化
アンチモン、四塩化チタン、四塩化スズ、三フッ化ホウ
素、三塩化アルミニウム、三塩化鉄の如きルイス酸、又
はこれらと無水酢酸、有機スルフィド酸等との有機錯
体、あるいは有機亜鉛化合物、有機アルミニウム化合物
等の有機金属化合物等である。As the cation catalyst, antimony pentachloride, antimony pentafluoride, titanium tetrachloride, tin tetrachloride, boron trifluoride, aluminum trichloride, Lewis acid such as iron trichloride, or these and acetic anhydride, organic sulfide acid and the like. Or an organic metal compound such as an organic zinc compound or an organic aluminum compound.
本発明の新規化合物は、分子内に重合時非収縮性基
（スピロオルトエステル基）を有し、更にポリフルオロ
アルキル基を有することから、撥水撥油剤、離型剤、剥
離剤等の表面改質剤の他、封止樹脂、接着剤等の原料と
して有用である。INDUSTRIAL APPLICABILITY The novel compound of the present invention has a non-contractile group (spiro-orthoester group) during polymerization in the molecule and further has a polyfluoroalkyl group, so that the surface of a water / oil repellent agent, a release agent, a release agent, etc. In addition to the modifier, it is useful as a raw material for sealing resin, adhesive, and the like.
［実施例］ 参考例；「含フッ素エポキシドの製造法」 100ml三ツ口フラスコに、ｎ−C8F17CH2CH2OH46.42g
（100mmol）、エピクロロヒドリン13.99g（150mmol）水
酸化ナトリウム4.4g（110mmol）、水1.65g加え、室温で
12時間撹拌した。その後反応物をエーテル抽出し、有機
層を無水硫酸マグネシウムで一夜乾燥した後、減圧蒸留
し、６−パーフルオロオクチル−1,2−エポキシ−４−
オキサヘキサンを15.47g（収率30％）得た。（沸点79〜
88℃/1mmHg、無色透明液体） （実施例−１） 窒素置換した50ml−二ツ口フラスコに、ε−カプロラ
クトン2.05g（18mmol）と、四塩化炭素7.5gを加え、０
℃に保ち撹拌しながら、三フッ化ホウ素エーテル錯体0.
132ml（1.08mmol6mol％）を加えた後、7.5gの四塩化炭
素に溶かした６−パーフルオロオクチル−1,2−エポキ
シ−４−オキサヘキサン9.35g（18mmol）を１時間かけ
て滴下した。更に０〜５℃で６時間反応させた後、トリ
エチルアミン0.15ml（1.08mmol、6mol％）を加え反応を
停止させ、１−規定水酸化ナトリウム水溶液で洗浄し、
有機層を無水硫酸マグネシウムで一夜乾燥後、減圧蒸留
し、２−［２−パーフルオロオクチル）エトキシメチ
ル］−1,4,6−トリオキサスピロ［4.6］ウンデカンを収
量5.46g、収率48％で得た。（沸点100℃/0.2mmHg、白色
固体）２−［２−（パーフルオロオクチル）エトキシメ
チル］−1,4,6−トリオキサスピロ［4.6］ウンデカンの
スペクトルデータ 1H NMR（60MHz,CCl4） δ 4.43〜3.18（m,9H,ｂ，ｃ，ｄ，ｅ，ｆ） δ 2.99〜1.27（m,10H,ａ，ｇ，ｈ，ｉ，ｊ） IR（neat）［cm-1］ 2930（−CH2−）,1240,1205,1145（−CF2,−CF3）,147
5,1070,1040,960［SOE（スピロオルトエステル）特性吸
収］[Example] Reference Example; the 100ml three-neck flask 'method of producing a fluorine-containing epoxide ", n-C 8 F 17 CH 2 CH 2 OH46.42g
(100 mmol), epichlorohydrin 13.99 g (150 mmol) sodium hydroxide 4.4 g (110 mmol), water 1.65 g, at room temperature
It was stirred for 12 hours. Thereafter, the reaction product was extracted with ether, and the organic layer was dried over anhydrous magnesium sulfate overnight and distilled under reduced pressure to give 6-perfluorooctyl-1,2-epoxy-4-.
15.47 g (yield 30%) of oxahexane was obtained. (Boiling point 79 ~
88 ° C./1 mmHg, colorless transparent liquid) (Example-1) To a 50 ml-necked flask with nitrogen substitution, 2.05 g (18 mmol) of ε-caprolactone and 7.5 g of carbon tetrachloride were added, and 0
Boron trifluoride ether complex 0.
After adding 132 ml (1.08 mmol 6 mol%), 9.35 g (18 mmol) of 6-perfluorooctyl-1,2-epoxy-4-oxahexane dissolved in 7.5 g of carbon tetrachloride was added dropwise over 1 hour. After further reacting at 0 to 5 ° C for 6 hours, 0.15 ml (1.08 mmol, 6 mol%) of triethylamine was added to stop the reaction, and the mixture was washed with a 1-normal sodium hydroxide aqueous solution,
The organic layer was dried over anhydrous magnesium sulfate overnight and distilled under reduced pressure to give 2- [2-perfluorooctyl) ethoxymethyl] -1,4,6-trioxaspiro [4.6] undecane (5.46 g, yield 48%). Got with. (Boiling point 100 ° C / 0.2mmHg, white solid) Spectral data of 2- [2- (perfluorooctyl) ethoxymethyl] -1,4,6-trioxaspiro [4.6] undecane 1 H NMR (60 MHz, CCl 4 ) δ 4.43 to 3.18 (m, 9H, b , c , d , e , f ) δ 2.99 to 1.27 (m, 10H, a , g , h , i , j ) IR (neat ) [Cm -1 ] 2930 (-CH 2- ), 1240, 1205, 1145 (-CF 2 , -CF 3 ), 147
5,1070,1040,960 [SOE (Spiro orthoester) characteristic absorption]
Claims (1)
ピロオルトエステル。 （式中、RfはC8F17−を示す。）1. A fluorine-containing spiro orthoester represented by the following general formula (I). (In the formula, Rf represents C 8 F 17 −.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62128416A JP2532095B2 (en) | 1987-05-27 | 1987-05-27 | Fluorine-containing spiro orthoester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62128416A JP2532095B2 (en) | 1987-05-27 | 1987-05-27 | Fluorine-containing spiro orthoester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63295586A JPS63295586A (en) | 1988-12-01 |
| JP2532095B2 true JP2532095B2 (en) | 1996-09-11 |
Family
ID=14984221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62128416A Expired - Lifetime JP2532095B2 (en) | 1987-05-27 | 1987-05-27 | Fluorine-containing spiro orthoester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2532095B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101779088B1 (en) | 2016-04-27 | 2017-09-19 | 주식회사 제일화성 | Method for manufacturing insulating material using resin composition having hydrophobicity |
-
1987
- 1987-05-27 JP JP62128416A patent/JP2532095B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101779088B1 (en) | 2016-04-27 | 2017-09-19 | 주식회사 제일화성 | Method for manufacturing insulating material using resin composition having hydrophobicity |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63295586A (en) | 1988-12-01 |
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