JPH072837B2 - Method for producing trifluoropropylene oxide polymer - Google Patents
Method for producing trifluoropropylene oxide polymerInfo
- Publication number
- JPH072837B2 JPH072837B2 JP10158190A JP10158190A JPH072837B2 JP H072837 B2 JPH072837 B2 JP H072837B2 JP 10158190 A JP10158190 A JP 10158190A JP 10158190 A JP10158190 A JP 10158190A JP H072837 B2 JPH072837 B2 JP H072837B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- trifluoropropylene oxide
- producing
- trifluoropropylene
- polymerization
- 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
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は含弗素エポキシド重合体の製造方法に関する。
更に詳しくは、アルカリ金属アルコキシドを重合開始剤
としてトリフルオロプロピレンオキシド重合体を製造す
る方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a fluorine-containing epoxide polymer.
More specifically, it relates to a method for producing a trifluoropropylene oxide polymer using an alkali metal alkoxide as a polymerization initiator.
［従来の技術］ トリフルオロプロピレンオキシド重合体は化学的に安定
なトリフルオロメチル基を持ったポリエーテルであり、
分子量によりその性状は異なるが、低分子量の重合体に
おいてもそのユニークな物性のために、潤滑油、界面活
性剤製造の中間体として、あるいは特殊ゴム製造の中間
体等として有用である。しかしトリフルオロプロピレン
オキシドの重合体を得るのは困難とされ、これまで各種
の開始剤による重合が試みられたが、重合体が得られた
例としては、塩化第２鉄、塩化アルミニウムなど、わず
かな例が知られているに過ぎなかった。[Prior Art] A trifluoropropylene oxide polymer is a polyether having a chemically stable trifluoromethyl group,
Although the properties vary depending on the molecular weight, even a low molecular weight polymer is useful as an intermediate for the production of lubricating oils and surfactants or as an intermediate for the production of special rubbers because of its unique physical properties. However, it has been difficult to obtain a polymer of trifluoropropylene oxide, and polymerization with various initiators has been tried so far. Examples of the polymer obtained include ferric chloride and aluminum chloride. Only examples were known.
［発明が解決しようとする課題］ 本発明者らは、潤滑油等の用途に適するトリフルオロプ
ロピレンオキシド重合体を得る方法について検討した結
果、アルカリ金属アルコキシドを触媒としてトリフルオ
ロプロピレンオキシドを重合させることにより、トリフ
ルオロプロピレンオキシド重合体が高収率で得られるこ
とを見出し、本発明に到達した。[Problems to be Solved by the Invention] The present inventors have studied a method for obtaining a trifluoropropylene oxide polymer suitable for applications such as lubricating oil, and as a result, polymerized trifluoropropylene oxide using an alkali metal alkoxide as a catalyst. As a result, they have found that a trifluoropropylene oxide polymer can be obtained in a high yield, and have reached the present invention.
［課題を解決するための手段］ 本発明はアルカリ金属アルコキシドの存在下でトリフル
オロプロピレンオキシドを重合させることを特徴とする
トリフルオロプロピレンオキシド重合体の製造方法であ
る。[Means for Solving the Problems] The present invention is a method for producing a trifluoropropylene oxide polymer, which comprises polymerizing trifluoropropylene oxide in the presence of an alkali metal alkoxide.
本発明方法において単量体として用いるトリフルオロプ
ロピレンオキシドは式 を有する化合物で、トリフルオロアセトンを臭素化して
得られたブロモトリフルオロアセトンを水素化リチウム
アルミニウムで還元してブロモトリフルオロイソプロピ
ルアルコールを苛性ソーダで処理する方法、あるいはト
リフルオロプロピレンを微生物を用いて酸化する方法
（特公昭61−14798号公報、特開昭61−202697号公報参
照）などにより製造することができる。The trifluoropropylene oxide used as a monomer in the method of the present invention has the formula Of bromotrifluoroacetone obtained by brominating trifluoroacetone with lithium aluminum hydride and treating bromotrifluoroisopropyl alcohol with caustic soda, or oxidizing trifluoropropylene using a microorganism. (See Japanese Patent Publication No. 61-14798, JP-A No. 61-202697) and the like.
本発明において開始剤として使用するアルカリ金属アル
コキシドはナトリウム、カリウム、ルビジウム、セシウ
ム、リチウム等の金属アルコキシドであるが、特にカリ
ウム、ルビジウム、セシウムのアルコキシドが好まし
い。アルコキシドとしては、メトキサイド、エトキサイ
ド、プロポキサイド、ブトキサイド等を挙げることがで
きるが、特にブトキサイドが好適である。The alkali metal alkoxide used as an initiator in the present invention is a metal alkoxide of sodium, potassium, rubidium, cesium, lithium or the like, and potassium, rubidium or cesium alkoxide is particularly preferable. Examples of the alkoxide include methoxide, ethoxide, propoxide and butoxide, but butoxide is particularly preferable.
アルカリ金属アルコキシドの使用量は、モノマーに対し
0.1％〜10％特に0.5％〜５％が好ましい。The amount of alkali metal alkoxide used is
0.1% to 10%, particularly 0.5% to 5% is preferable.
重合は有機溶媒の存在下で行なうのが好適であり、溶媒
としては、ベンゼン、トルエン、キシレン等の芳香族炭
化水素や1,2−ジメトキシエタン等のエーテル類が好適
であり、特にベンゼンおよび1,2−ジメトキシエタン溶
媒中で重合を行なうと高い重合収率が得られるので好ま
しい。The polymerization is preferably carried out in the presence of an organic solvent, and as the solvent, aromatic hydrocarbons such as benzene, toluene, xylene and ethers such as 1,2-dimethoxyethane are preferable, and benzene and 1 are particularly preferable. Polymerization in a 2,2-dimethoxyethane solvent is preferable because a high polymerization yield can be obtained.
重合温度は−80℃〜200℃、特に−20℃〜120℃が好まし
い。重合は窒素等の不活性ガス中で行なう。The polymerization temperature is preferably -80 ° C to 200 ° C, particularly preferably -20 ° C to 120 ° C. Polymerization is carried out in an inert gas such as nitrogen.
反応が完結した後、塩酸、硫酸などの酸で反応を停止さ
せ、メタノール等で洗浄し、メタノールを除去し、更に
洗浄、濾過し、減圧乾燥することによりポリマーが得ら
れる。After the reaction is completed, the reaction is stopped with an acid such as hydrochloric acid or sulfuric acid, washed with methanol or the like to remove methanol, further washed, filtered, and dried under reduced pressure to obtain a polymer.
［実施例］ 以下に実施例を挙げて本発明を具体的に説明する。[Examples] The present invention will be specifically described below with reference to Examples.
実施例１ トリフルオロプロピレンを特公昭61−14798号記載の方
法により、微生物で酸化して得られたトリフルオロプロ
ピレンオキシドを窒素気流下で蒸留して精製モノマーを
得た。Example 1 Trifluoropropylene oxide obtained by oxidizing trifluoropropylene with a microorganism according to the method described in JP-B-61-14798 was distilled under a nitrogen stream to obtain a purified monomer.
上記精製モノマー1.2ml（14.03mmol）と、重合開始剤と
してカリウムターシャリーブトキサイドおよび溶媒とし
てベンゼン8mlとを窒素置換した30ml容アンプルに充填
した。開始剤の添加量は0.234mmolで、モノマー：開始
剤＝50:1の仕込比（モル比）とした。アンプルを密封後
反応温度80℃で３日間重合を行なった。1.2 ml (14.03 mmol) of the above purified monomer, potassium tertiary butoxide as a polymerization initiator, and 8 ml of benzene as a solvent were charged in a nitrogen-substituted 30 ml ampoule. The amount of the initiator added was 0.234 mmol, and the charging ratio (molar ratio) was monomer: initiator = 50: 1. After sealing the ampoule, polymerization was carried out at a reaction temperature of 80 ° C. for 3 days.
反応終了後、アンプル管を開封し、メタノール塩酸を加
えて反応を停止させ、反応生成物をメタノール中に移し
たが沈殿は生じなかった。ついでメタノールを蒸発除去
し、残留ポリマーに希塩酸を加え、超音波で15分間処理
し、ついで硝子フィルターで濾過し蒸留水およびメタノ
ールでポリマーを洗浄し、減圧乾燥して無色油状の精製
ポリマーが得られた。ポリマーの性状、収量および収率
を表１に示す。After completion of the reaction, the ampoule tube was opened, methanol hydrochloric acid was added to stop the reaction, and the reaction product was transferred into methanol, but no precipitation occurred. Then, methanol was removed by evaporation, dilute hydrochloric acid was added to the residual polymer, treated with ultrasonic waves for 15 minutes, then filtered through a glass filter, the polymer was washed with distilled water and methanol, and dried under reduced pressure to obtain a colorless oily purified polymer. It was The properties, yields and yields of the polymers are shown in Table 1.
得られたポリマーのGPCピーク分子量は4.3×103であっ
た。The GPC peak molecular weight of the obtained polymer was 4.3 × 10 3 .
ポリマーの13C NMRスペクトル（JEOL270MHz−NMR）は
第１図に示されるように118〜131ppm（ａ）にCF3基
（ｑ）,79ppm付近（ｂ）にCH（ｑ）,71ppm付近（ｃ）に
CH2の炭素によるシグナルが認められ、CF3基を有するポ
リエーテルが生成していることが確認された。As shown in FIG. 1, the 13 C NMR spectrum (JEOL270MHz-NMR) of the polymer is 118 to 131 ppm (a), CF 3 group (q), 79 ppm (b), CH (q), 71 ppm (c). To
A signal due to the carbon of CH 2 was observed, and it was confirmed that a polyether having a CF 3 group was produced.
実施例２〜11 重合開始剤として表１に示す各種のアルカリ金属アルコ
キシドおよび表１に示す溶媒を用い、重合温度を表１の
温度とした以外は、実施例１と同様にして重合を行なっ
た。但し重合開始剤の添加量はいずれも0.234mmolとし
モノマー：開始剤＝50:1の仕込比（モル比）とした。Examples 2 to 11 Polymerization was carried out in the same manner as in Example 1 except that the various alkali metal alkoxides shown in Table 1 and the solvents shown in Table 1 were used as the polymerization initiator and the polymerization temperature was set to the temperature shown in Table 1. . However, the addition amount of each of the polymerization initiators was 0.234 mmol, and the charging ratio (molar ratio) was monomer: initiator = 50: 1.
反応終了後、得られたポリマーを実施例１と同じ方法で
処理し、精製ポリマーが得られた。ポリマーの性状、収
率を表１に示す。After completion of the reaction, the obtained polymer was treated in the same manner as in Example 1 to obtain a purified polymer. Table 1 shows the polymer properties and yields.
［発明の効果］ 本発明によれば分子内にトリフルオロメチル基を含有す
るトリフルオロプロピレンオキシドの低分子量の重合体
が高収率で得られるので、高性能の潤滑油、界面活性
剤、特殊ゴム法の製法として利用価値が大きい。 EFFECTS OF THE INVENTION According to the present invention, a low-molecular weight polymer of trifluoropropylene oxide containing a trifluoromethyl group in the molecule can be obtained in a high yield, so that a high-performance lubricating oil, a surfactant, a special It has great utility as a rubber manufacturing method.
第１図は本発明方法により得られたトリフルオロプロピ
レンオキシド重合体の13C NMRスペクトルである。FIG. 1 is a 13 C NMR spectrum of a trifluoropropylene oxide polymer obtained by the method of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 Ｐｏｌｙｍ．Ｐｒｅｐｒ．，Ａｍ．Ｃｈ ｅｍ．Ｓｏｃ．，Ｄｉｖ．Ｐｏｌｙｍ．Ｃ ｈｅｍ．（1967），８（１），491−495 ─────────────────────────────────────────────────── ─── Continued Front Page (56) References Polym. Prepr. , Am. Ch em. Soc. , Div. Polym. Chem. (1967), 8 (1), 491-495.
Claims (1)
フルオロプロピレンオキシドを重合させることを特徴と
するトリフルオロプロピレンオキシド重合体の製造法。1. A method for producing a trifluoropropylene oxide polymer, which comprises polymerizing trifluoropropylene oxide in the presence of an alkali metal alkoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10158190A JPH072837B2 (en) | 1990-04-19 | 1990-04-19 | Method for producing trifluoropropylene oxide polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10158190A JPH072837B2 (en) | 1990-04-19 | 1990-04-19 | Method for producing trifluoropropylene oxide polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH041230A JPH041230A (en) | 1992-01-06 |
| JPH072837B2 true JPH072837B2 (en) | 1995-01-18 |
Family
ID=14304359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10158190A Expired - Lifetime JPH072837B2 (en) | 1990-04-19 | 1990-04-19 | Method for producing trifluoropropylene oxide polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH072837B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649348A (en) * | 1992-08-04 | 1994-02-22 | Shin Etsu Chem Co Ltd | Room temperature curing polyether composition |
| AU4811800A (en) * | 1999-05-04 | 2000-11-17 | E.I. Du Pont De Nemours And Company | Polyfluorinated epoxides and associated polymers and processes |
-
1990
- 1990-04-19 JP JP10158190A patent/JPH072837B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Ｐｏｌｙｍ．Ｐｒｅｐｒ．，Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，Ｄｉｖ．Ｐｏｌｙｍ．Ｃｈｅｍ．（１９６７），８（１），４９１−４９５ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH041230A (en) | 1992-01-06 |
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