JPH0617338B2 - Novel fluorine-containing polyester ester - Google Patents
Novel fluorine-containing polyester esterInfo
- Publication number
- JPH0617338B2 JPH0617338B2 JP16642286A JP16642286A JPH0617338B2 JP H0617338 B2 JPH0617338 B2 JP H0617338B2 JP 16642286 A JP16642286 A JP 16642286A JP 16642286 A JP16642286 A JP 16642286A JP H0617338 B2 JPH0617338 B2 JP H0617338B2
- Authority
- JP
- Japan
- Prior art keywords
- containing polyester
- novel fluorine
- polyester ester
- fluorine
- 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 - Fee Related
Links
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、新規含フッ素ポリエーテルエステルに関す
る。TECHNICAL FIELD The present invention relates to a novel fluorine-containing polyether ester.
［発明の構成］ 本発明は、一般式： ［式中、 Ｒは、炭素数２〜６の２価の脂肪族炭化水素基、ｎは、
１〜１０の整数を表す。］ で示される含フッ素ポリエーテルエステルを提供する。[Structure of the Invention] The present invention has the general formula: [In the formula, R is a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, and n is
It represents an integer of 1 to 10. ] The fluorine-containing polyether ester shown by these is provided.
本発明の含フッ素ポリエーテルエステルは、エポキシ樹
脂の原料等として利用できる。The fluorine-containing polyether ester of the present invention can be used as a raw material for epoxy resin.
本発明の含フッ素ポリエーテルエステルの具体例として
は、以下の化合物が挙げられる。The following compounds may be mentioned as specific examples of the fluorinated polyether ester of the present invention.
［上記式中、ｎは前記と同意義である。］ 本発明の化合物は、例えば、以下のようにして製造する
ことができる。 [In the above formula, n has the same meaning as described above. The compound of the present invention can be produced, for example, as follows.
式：ＨＯ−Ｒ′−ＯＨ ［式中、Ｒ′は、炭素数２〜６の２価の脂肪族炭化水素
基である。］ で示されるジオール、ＮａＨおよび非プロトン性溶媒
（好ましくはエーテル）の混合物に、２，２，３，３−
テトラフルオロオキセタンを、そのままあるいは溶媒で
希釈して滴下し、室温〜５０℃で数時間反応させる。生
成した沈澱（ＮａＦ）を濾去し、濾液から溶媒を留去
し、粗生成物を得る。場合によっては、この粗生成物に
メタノールなどのプロトン性溶媒を加え、冷却し、環状
物を析出させることにより、環状物と直鎖状物とを分離
することができる。Formula: HO-R'-OH [In formula, R'is a C2-C6 bivalent aliphatic hydrocarbon group. ] To a mixture of diol, NaH and an aprotic solvent (preferably ether) represented by
Tetrafluorooxetane is added as it is or after being diluted with a solvent and added dropwise, and reacted at room temperature to 50 ° C. for several hours. The formed precipitate (NaF) is filtered off and the solvent is distilled off from the filtrate to obtain a crude product. In some cases, a cyclic product and a linear product can be separated by adding a protic solvent such as methanol to this crude product, cooling and precipitating the cyclic product.
［実施例］ 以下に実施例を示す。[Examples] Examples are shown below.
実施例１ 塩化カルシウム乾燥管及び氷水コンデンサー付き３００
ml三つ口フラスコに水素化ナトリウム３．９ｇ（０．１
６モル）およびモノグライム２００mlを仕込んだ。撹拌
下室温でエチレングリコール５ｇ（０．０８モル）を滴
下した。さらに、２，２，３，３−テトラフルオロオキ
セタン１０．５ｇ（０．０８モル）をモノグライム５０
mlで希釈し、これを１時間かけて滴下し、滴下終了後、
室温で３時間反応させた。析出した沈澱を濾去し、濾液
からモノグライムを留去し、油状生成物を得た。さらに
油状生成物にメタノール１０mlを加え冷却し、沈澱を析
出させ、この沈澱を濾取し、環状物３．７ｇを得た。こ
の環状物は、 の１：１（ガスクロマトグラフイー）混合物であった。
又、濾液からメタノールを留去し、直鎖状オリゴマー
４．３ｇを得た。Example 1 300 with calcium chloride drying tube and ice water condenser
Sodium hydride 3.9g (0.1
6 mol) and 200 ml of monoglyme were charged. 5 g (0.08 mol) of ethylene glycol was added dropwise at room temperature with stirring. Further, 10.5 g (0.08 mol) of 2,2,3,3-tetrafluorooxetane was added to Monoglyme 50.
It is diluted with ml and added dropwise over 1 hour.
The reaction was carried out at room temperature for 3 hours. The deposited precipitate was filtered off, and monoglyme was distilled off from the filtrate to obtain an oily product. Further, 10 ml of methanol was added to the oily product and cooled to precipitate a precipitate, and the precipitate was collected by filtration to obtain 3.7 g of a cyclic product. This ring is 1: 1 (gas chromatograph) mixture.
Further, methanol was distilled off from the filtrate to obtain 4.3 g of a linear oligomer.
二種の環状物の分析結果は以下の通りであった。The analysis results of the two kinds of cyclic substances are as follows.
ＩＲ（KBr）：２９００，１７８０，１４６０，１２５
０，１１４０cm１。IR (KBr): 2900, 1780, 1460, 125
0.1140 cm 1 .
ガスクロマトグラフー質量分析： （ガスクロマトグラフ条件：カラム ＳＥ−３０、３φ
×２ｍ、５０℃から１００℃（昇温速度１０℃／分、キ
ャリアガス ヘリウム３０ml／分）） (i) ガスクロマトグラフ保持時間：１５．９分 質量分析：３０５（Ｍ＋Ｈ）、２８４（Ｍ−ＨＦ）、 ２４４（CH2CF2C（＝Ｏ）OCH2CH2OC（＝Ｏ）CF2CH2）、 ６４（ＣＨ２ＣＦ２）、６０（ＯＣＨ２ＣＨ２Ｏ） （ii） ガスクロマトグラフ保持時間：１６．３分 質量分析：３０５（Ｍ＋Ｈ）、２８４（Ｍ−ＨＦ）、 １５２（ＣＨ２ＣＦ２Ｃ（＝Ｏ）ＯＣＨ２ＣＨ２Ｏ）、 ６４（ＣＨ２ＣＦ２）、 元素分析（二種とも同じ）： Ｈ Ｃ Ｆ （計算値） ３．９４ ３９．４７ ２５．０ （実測値） ３．０８ ３９．３０ ２４．６３。Gas chromatograph / mass spectrometry: (Gas chromatograph conditions: column SE-30, 3φ
× 2m, 50 ° C to 100 ° C (heating rate 10 ° C / min, carrier gas helium 30 ml / min) (i) Gas chromatographic retention time: 15.9 minutes Mass spectrometry: 305 (M + H), 284 (M-HF), 244 (CH 2 CF 2 C (= O) OCH 2 CH 2 OC (= O) CF 2 CH 2), 64 (CH 2 CF 2 ), 60 (OCH 2 CH 2 O) (ii) Gas chromatographic retention time: 16.3 minutes Mass spectrometry: 305 (M + H), 284 (M-HF), 152 (CH 2 CF 2 C (= O) OCH 2 CH 2 O), 64 (CH 2 CF 2), Elemental analysis (same for both types): HCF (calculated value) 3.94 39.47 25.0 (measured value) 3.08 39.30 24.63.
直鎖状オリゴマーの平均分子量は、平衡蒸気圧法によれ
ば、約９６０（平均重合度：６．３）であった。The average molecular weight of the linear oligomer was about 960 (average degree of polymerization: 6.3) according to the equilibrium vapor pressure method.
実施例２ 塩化カルシウム乾燥管及び氷水コンデンサー付き３００
ml三つ口フラスコに、水素ナトリウム２．７ｇ（０．１
１モル）およびモノグライム２５０mlを仕込んだ。撹拌
しながら室温で１，４−ブタンジオール５．０ｇ（０．
０５６モル）を滴下した。さらに２，２，３，３−テト
ラフルオロオキセタン７．３ｇ（０．０５６モル）をモ
ノグライム５０mlで希釈し、これを約１時間かけて滴下
し、滴下終了後、室温で約１０時間反応を続けた。析出
した沈澱を濾去し、蒸留により濾液を約mlまで濃縮した
後、撹拌下、５００mlの純水に加えた。析出した沈澱を
濾取し、白色固形物約８ｇを得た。白色固形物は、環状
物 の１：１（ガスクロマトグラフ）混合物であった。又、
濾液から水を留去し、直鎖状オリゴマー２．４ｇを得
た。Example 2 300 with calcium chloride drying tube and ice water condenser
2.7 ml of sodium hydrogen (0.1 g
1 mol) and 250 ml of monoglyme were charged. 5.0 g of 1,4-butanediol (0.
(056 mol) was added dropwise. Furthermore, 7.3 g (0.056 mol) of 2,2,3,3-tetrafluorooxetane was diluted with 50 ml of monoglyme and added dropwise over about 1 hour. After completion of the addition, the reaction was continued at room temperature for about 10 hours. It was The deposited precipitate was filtered off, the filtrate was concentrated to about ml by distillation, and then added to 500 ml of pure water with stirring. The deposited precipitate was collected by filtration to obtain about 8 g of a white solid. White solid is a ring 1: 1 (gas chromatograph) mixture. or,
Water was distilled off from the filtrate to obtain 2.4 g of a linear oligomer.
二種の環状物の分析結果は以下の通りであった。The analysis results of the two kinds of cyclic substances are as follows.
ＩＲ（KBr）（二種とも同じ）：２９５０，１７７０，
１４８０，１２５０，１１５０cm１。IR (KBr) (same for both): 2950, 1770,
1480, 1250, 1150 cm 1 .
ガスクロマトグラフー質量分析： （ガスクロマトグラフ条件：カラム ＳＥ−３０、３φ
×２ｍ、５０℃から２００℃（昇温速度１０℃／分、キ
ャリアガス ヘリウム３０ml／分） (i) ガスクロマトグラフ保持時間：２３．６分 質量分析：３６１（Ｍ＋Ｈ）、３４１（Ｍ−ＨＦ）、 ２７２（CH2CF2C（＝Ｏ）OCH2CH2CH2CH2OC（＝Ｏ）CF2C
H2）、 ８８（ＯＣＦ２ＣＨ２ＣＨ２ＣＨ２Ｏ）、６４（ＣＨ２
ＣＦ２） （ii） ガスクロマトグラフ保持時間：２４．１分 質量分析：３６１（Ｍ＋Ｈ）、３４１（Ｍ−ＨＦ）、 １８０（ＣＨ２ＯＣ（＝Ｏ）ＣＦ２ＣＨ２ＯＣＨ２ＣＨ
２ＣＨ２） ６４（ＣＨ２ＣＦ２）、１ Ｈ−ＮＭＲ（アセトンｄ６（二種とも同じ） δ（ppm＝７．３（８Ｈ，ｍ），３．５０（４Ｈ，
ｔ），３．８３（４Ｈ，ｔ），４．２５（４Ｈ，ｔ）。１９ Ｆ−ＮＭＲ（アセトンｄ６）二種とも同じ）： δ（ppm）＝３５．２(t)。Gas chromatograph / mass spectrometry: (Gas chromatograph conditions: column SE-30, 3φ
× 2m, 50 ° C to 200 ° C (temperature rising rate 10 ° C / min, carrier gas helium 30 ml / min) (i) Gas chromatographic retention time: 23.6 minutes Mass spectrometry: 361 (M + H), 341 (M-HF), 272 (CH 2 CF 2 C (= O) OCH 2 CH 2 CH 2 CH 2 OC (= O) CF 2 C
H 2 ), 88 (OCF 2 CH 2 CH 2 CH 2 O), 64 (CH 2
CF 2 ) (ii) Gas chromatographic retention time: 24.1 minutes Mass spectrometry: 361 (M + H), 341 (M-HF), 180 (CH 2 OC (= O) CF 2 CH 2 OCH 2 CH
2 CH 2 ) 64 (CH 2 CF 2 ), 1 H-NMR (acetone d 6 (both are the same) δ (ppm = 7.3 (8 H, m), 3.50 (4 H,
t), 3.83 (4H, t), 4.25 (4H, t). 19 F-NMR (acetone d 6 ) both are the same): δ (ppm) = 35.2 (t).
元素分析（二種とも同じ）： Ｈ Ｃ Ｆ （計算値） ５．５６ ４６．６７ ２１．１１ （実測値） ６．０２ ４６．２３ ２０．０９ 直鎖状オリゴマーの平均分子量は、平衡蒸気圧法によれ
ば、１２００であった。Elemental analysis (same for both types): HCF (calculated value) 5.56 46.67 21.11 (measured value) 6.02 46.23 20.09 The average molecular weight of the linear oligomer is the equilibrium vapor pressure method. It was 1200.
Claims (1)
１〜１０の整数を表す。］ で示される含フッ素ポリエーテルエステル。1. A general formula: [In the formula, R is a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, and n is
It represents an integer of 1 to 10. ] Fluorine-containing polyether ester shown by these.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16642286A JPH0617338B2 (en) | 1986-07-14 | 1986-07-14 | Novel fluorine-containing polyester ester |
| JP5102341A JPH0776220B2 (en) | 1986-07-14 | 1993-04-28 | Novel fluorinated polyether ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16642286A JPH0617338B2 (en) | 1986-07-14 | 1986-07-14 | Novel fluorine-containing polyester ester |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5102341A Division JPH0776220B2 (en) | 1986-07-14 | 1993-04-28 | Novel fluorinated polyether ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6322539A JPS6322539A (en) | 1988-01-30 |
| JPH0617338B2 true JPH0617338B2 (en) | 1994-03-09 |
Family
ID=15831128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16642286A Expired - Fee Related JPH0617338B2 (en) | 1986-07-14 | 1986-07-14 | Novel fluorine-containing polyester ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0617338B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220259132A1 (en) * | 2019-09-30 | 2022-08-18 | Daikin Industries, Ltd. | Method for producing propionic acid derivative |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0283457U (en) * | 1988-12-14 | 1990-06-28 |
-
1986
- 1986-07-14 JP JP16642286A patent/JPH0617338B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220259132A1 (en) * | 2019-09-30 | 2022-08-18 | Daikin Industries, Ltd. | Method for producing propionic acid derivative |
| US11945773B2 (en) * | 2019-09-30 | 2024-04-02 | Daikin Industries, Ltd. | Method for producing propionic acid derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6322539A (en) | 1988-01-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |