JPH07149889A - Production of fluorine-containing alkyl polyether polymer - Google Patents
Production of fluorine-containing alkyl polyether polymerInfo
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- JPH07149889A JPH07149889A JP30012993A JP30012993A JPH07149889A JP H07149889 A JPH07149889 A JP H07149889A JP 30012993 A JP30012993 A JP 30012993A JP 30012993 A JP30012993 A JP 30012993A JP H07149889 A JPH07149889 A JP H07149889A
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- Prior art keywords
- oxide
- molecular weight
- fluorine
- polymer
- metal complex
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、含フッ素アルキルポリ
エーテル重合体の製造方法に関する。更に詳しくは、ポ
ルフィリン金属錯体を触媒として含フッ素アルキルポリ
エーテル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 alkyl polyether polymer. More specifically, it relates to a method for producing a fluorine-containing alkyl polyether polymer using a porphyrin metal complex as a catalyst.
【０００２】[0002]
【従来の技術】含フッ素アルキルポリエーテル重合体は
化学的に安定なパーフルオロアルキル基を持ったポリエ
ーテルであり、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。パーフルオロアルキレンオキシドの重合体を得るた
めの開始剤としては、フッ化セシウム、フッ化カリウム
などの１価の金属フッ化物などが知られているが、得ら
れる重合体の分子量は低く分子量分布も広いため実用に
際しては精製などにコストがかかり高価になってしま
う。2. Description of the Related Art Fluorine-containing alkyl polyether polymers are chemically stable polyethers having perfluoroalkyl groups, and are used as intermediates in the production of lubricating oils and surfactants, or in the production of special rubbers. Is useful as As the initiator for obtaining the polymer of perfluoroalkylene oxide, monovalent metal fluorides such as cesium fluoride and potassium fluoride are known, but the obtained polymer has a low molecular weight and also has a molecular weight distribution. Since it is wide, purification and other costs are high in practical use, which makes it expensive.
【０００３】一方、アルキレンオキシドの重合体を得る
ために用いられるポルフィリン金属錯体は、パーフルオ
ロアルキレンオキシド単独の重合触媒としては全く効果
が無かった。On the other hand, the porphyrin metal complex used to obtain a polymer of alkylene oxide has no effect as a polymerization catalyst of perfluoroalkylene oxide alone.
【０００４】[0004]
【発明が解決しようとする課題】潤滑油などに用いられ
る含フッ素アルキルポリエーテル重合体は、化学的に安
定である事が望まれている。また、その他にも分子量の
低いものが含まれているとそれが低沸物となるために精
製が必要となるなどの問題があるため、分子量が高く、
分子量分布の狭いものが望まれていた。SUMMARY OF THE INVENTION It is desired that the fluorine-containing alkyl polyether polymer used for lubricating oil or the like be chemically stable. In addition, in addition to that, if a substance having a low molecular weight is contained, it becomes a low boiling point and thus there is a problem that purification is required, so that the molecular weight is high,
A narrow molecular weight distribution was desired.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記技術課
題を解決すべく、さまざまな触媒を検討した結果、ポル
フィリン金属錯体を触媒として、パーフルオロアルキレ
ンオキシドとアルキレンオキシドを共重合させる事によ
って分子量が高く、しかも分子量分布の狭い含フッ素ア
ルキルポリエーテル重合体が得られる事を見出し、本発
明を完成するに至った。Means for Solving the Problems The present inventors have studied various catalysts in order to solve the above technical problems, and as a result, by copolymerizing perfluoroalkylene oxide and alkylene oxide with a porphyrin metal complex as a catalyst, The inventors have found that a fluorine-containing alkyl polyether polymer having a high molecular weight and a narrow molecular weight distribution can be obtained, and completed the present invention.
【０００６】即ち、本発明はポリフィリン金属錯体の存
在下で、パーフルオロアルキレンオキシドとアルキレン
オキシドを共重合させることを特徴とする含フッ素アル
キルポリエーテル重合体の製造方法である。That is, the present invention is a method for producing a fluorine-containing alkyl polyether polymer, which comprises copolymerizing perfluoroalkylene oxide and alkylene oxide in the presence of a porphyrin metal complex.
【０００７】本発明におけるポルフィリン金属錯体は、
公知の化合物を何ら制限なく用いることができる。本発
明で好適に用い得るポルフィリン金属錯体はポルフィリ
ンアルミニウム錯体およびポルフィリン亜鉛錯体であ
り、下記式〔Ｉ〕及び〔ＩＩ〕で示すことができる。The porphyrin metal complex in the present invention is
Known compounds can be used without any limitation. Porphyrin metal complexes that can be preferably used in the present invention are porphyrin aluminum complexes and porphyrin zinc complexes, which can be represented by the following formulas [I] and [II].
【０００８】[0008]
【化１】 [Chemical 1]
【０００９】[0009]
【化２】 [Chemical 2]
【００１０】（式中、Ｒ1〜Ｒ12は水素原子、置換若し
くは非置換の炭化水素基であり、Ｒ3とＲ4，Ｒ6とＲ7，
Ｒ9とＲ10及びＲ12とＲ1は夫々縮合環を形成していても
良く、Ｒは炭化水素基であり、Ｘは水素原子、ハロゲン
原子、アルキル基、アルコキシ基、フェノキシ基、アル
キルチオ基又は水酸基である。）上記一般式Ｒ1〜Ｒ12
およびＲで示される炭化水素基としては、炭素数が１〜
１０の範囲であることが好ましく、アルキル基、アリー
ル基、アルキレン基、アルケニレン基等が採用される。
この内、置換炭化水素基の置換基としては、ハロゲン原
子やアルコキシ基が挙げられる。(In the formula, R 1 to R 12 are hydrogen atoms or substituted or unsubstituted hydrocarbon groups, and R 3 and R 4 , R 6 and R 7 ,
R 9 and R 10, and R 12 and R 1 may each form a condensed ring, R is a hydrocarbon group, and X is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenoxy group, an alkylthio group. Or it is a hydroxyl group. ) The above general formulas R 1 to R 12
And the hydrocarbon group represented by R has a carbon number of 1 to
It is preferably in the range of 10, and an alkyl group, an aryl group, an alkylene group, an alkenylene group or the like is adopted.
Among these, examples of the substituent of the substituted hydrocarbon group include a halogen atom and an alkoxy group.
【００１１】本発明に用いるポルフィリン金属錯体にお
ける金属としては、上記したアルミニウムおよび亜鉛の
他にマグネシウム、バナジウム、クロム、マンガン、
鉄、コバルト、ニッケル、銅、ルテニウム、ロジウム、
パラジウム、カドミウム等の金属を挙げることができ
る。The metals in the porphyrin metal complex used in the present invention include magnesium, vanadium, chromium, manganese, in addition to the above-mentioned aluminum and zinc.
Iron, cobalt, nickel, copper, ruthenium, rhodium,
Metals such as palladium and cadmium can be mentioned.
【００１２】本発明で好適に用いられるポルフィリン金
属錯体の具体例を示すと、テトラフェニルポルフィリン
アルミニウムクロリド、テトラベンズポルフィリンアル
ミニウムクロリド、テトラフェニルポルフィリンアルミ
ニウムメトキシド、テトラフェニルポルフィリンアルミ
ニウムメチル、テトラベンズポルフィリンアルミニウム
メチル、テトラフェニルポルフィリンアルミニウムエチ
ル、テトラキスペンタフルオロフェニルポルフィリンア
ルミニウムエチルなどのポルフィリンアルミニウム錯
体；ポリフィリン亜鉛錯体としてはテトラフェニルポル
フィリン亜鉛エチル、Ｎ−メチルテトラフェニルポルフ
ィリン亜鉛チオラート等のポルフィリン亜鉛錯体を挙げ
ることができる。Specific examples of the porphyrin metal complex preferably used in the present invention include tetraphenylporphyrin aluminum chloride, tetrabenzporphyrin aluminum chloride, tetraphenylporphyrin aluminum methoxide, tetraphenylporphyrin aluminum methyl, tetrabenzporphyrin aluminum methyl. , Porphyrin aluminum complexes such as tetraphenylporphyrin aluminum ethyl and tetrakispentafluorophenylporphyrin aluminum ethyl; examples of the polyphyrin zinc complex include porphyrin zinc complexes such as tetraphenylporphyrin zinc ethyl and N-methyltetraphenylporphyrin zinc thiolate.
【００１３】ポルフィリン金属錯体の使用量は一般の重
合反応における触媒量でよいが、パーフルオロアルキレ
ンオキシドとアルキレンオキシドの合計量１００重量部
に対して、０．１〜１０重量部、特に０．５〜５重量部
が好ましい。The amount of the porphyrin metal complex used may be a catalytic amount in a general polymerization reaction, but 0.1 to 10 parts by weight, particularly 0.5 to 100 parts by weight of the total amount of perfluoroalkylene oxide and alkylene oxide is used. -5 parts by weight is preferred.
【００１４】本発明におけるパーフルオロアルキレンオ
キシドは、公知のものであれば特に制限されず単独又は
ニ種以上を組み合わせて用いることができる。具体的に
は、ヘキサフルオロプロピレンオキシドやテトラフルオ
ロエチレンオキシドを挙げることができる。The perfluoroalkylene oxide in the present invention is not particularly limited as long as it is known, and it can be used alone or in combination of two or more kinds. Specific examples thereof include hexafluoropropylene oxide and tetrafluoroethylene oxide.
【００１５】本発明におけるアルキレンオキシドは、公
知のものであれば特に制限されず単独又はニ種以上を組
み合わせて用いることができる。具体的には、エチレン
オキシド、プロピレンオキシド、１−ブチレンオキシ
ド、エピクロルヒドリン、トリフルオロプロピレンオキ
シドのようなエポキシ基を有する脂肪族アルキレンオキ
シド；シクロペンテンオキシド、シクロヘキセンオキシ
ドのようなエポキシ基を有する脂環族アルキレンオキシ
ド；スチレンオキシドのようなエポキシ基を有する芳香
族アルキレンオキシド等を挙げることができ、その中で
も脂肪族アルキレンオキシドが好ましく、エチレンオキ
シド、プロピレンオキシドが特に好ましい。The alkylene oxide in the present invention is not particularly limited as long as it is a known one, and it can be used alone or in combination of two or more kinds. Specifically, an aliphatic alkylene oxide having an epoxy group such as ethylene oxide, propylene oxide, 1-butylene oxide, epichlorohydrin, and trifluoropropylene oxide; an alicyclic alkylene oxide having an epoxy group such as cyclopentene oxide and cyclohexene oxide. An aromatic alkylene oxide having an epoxy group such as styrene oxide and the like can be mentioned; among them, an aliphatic alkylene oxide is preferable, and ethylene oxide and propylene oxide are particularly preferable.
【００１６】パーフルオロアルキレンオキシドとアルキ
レンオキシドとの共重合割合は特に制限されるものでは
ないが、重合反応の進行および得られるアルキレンオキ
シドの単独重合体の生成を抑えるためには、パーフルオ
ロアルキレンオキシド１００重量部に対して、アルキレ
ンオキシドは１０〜１００重量部、好ましくは３０〜１
００重量部の範囲であることが好ましい。The copolymerization ratio of perfluoroalkylene oxide and alkylene oxide is not particularly limited, but in order to suppress the progress of the polymerization reaction and the formation of the obtained alkylene oxide homopolymer, perfluoroalkylene oxide is used. The alkylene oxide is 10 to 100 parts by weight, preferably 30 to 1 with respect to 100 parts by weight.
It is preferably in the range of 00 parts by weight.
【００１７】重合は無溶媒中あるいはベンゼン、トルエ
ン、キシレン等の芳香族炭化水素やジクロロメタン等の
ハロゲン系炭化水素等の有機溶媒の存在下で行ってもよ
い。重合温度は−３０〜２００℃、特に−２０〜１００
℃が好ましい。重合は窒素等の不活性ガス中で行なわれ
る。反応が完結した後、酢酸、塩酸などの酸で反応を停
止させ、メタノール、水等で洗浄し、減圧乾燥すること
により乾燥ポリマーが得られる。The polymerization may be carried out in the absence of a solvent or in the presence of an organic solvent such as an aromatic hydrocarbon such as benzene, toluene, xylene or a halogenated hydrocarbon such as dichloromethane. The polymerization temperature is −30 to 200 ° C., especially −20 to 100 ° C.
C is preferred. Polymerization is carried out in an inert gas such as nitrogen. After the reaction is completed, the reaction is stopped with an acid such as acetic acid or hydrochloric acid, washed with methanol, water or the like, and dried under reduced pressure to obtain a dry polymer.
【００１８】[0018]
【発明の効果】本発明の製造方法を用いる事により、潤
滑油などに求められる化学的に安定であり、しかも高分
子量で分子量分布の狭い含フッ素アルキルポリエーテル
重合体を得る事ができる。この結果、生成中に低沸物な
どの不純物が殆んど無いため、分離精製工程を省略する
事が可能となった。EFFECTS OF THE INVENTION By using the production method of the present invention, it is possible to obtain a fluorine-containing alkyl polyether polymer which is required for a lubricating oil and the like and which is chemically stable and has a high molecular weight and a narrow molecular weight distribution. As a result, it was possible to omit the separation and purification step because impurities such as low-boiling substances were scarcely present during production.
【００１９】[0019]
【実施例】以下に実施例を掲げて本発明を具体的に説明
するが、本発明はこれらの実施例に限定されるものでな
い。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
【００２０】実施例１ １００ｍｌ容量の耐圧製ガラスオートクレーブにテトラ
フェニルポルフィリン０．１２ｇ（０．２ｍｍｏｌ）と
ジエチルアルミニウムクロリド０．０２４ｇ（０．２ｍ
ｍｏｌ）、塩化メチレン５ｍｌを加え攪拌しながら３時
間反応させた後、未反応のジエチルアルミニウムクロリ
ドを除去するために５０℃で３時間真空乾燥した。次
に、容器をドライアイス−メタノールで冷却した状態
で、ヘキサフルオロプロピレンオキシド１７ｇ、プロピ
レンオキサイド６ｇを導入し１時間攪拌後０℃まで温度
を上昇させ、氷冷下１６時間反応させた。反応後、容器
を室温に戻しエバポレーターで未反応原料を留去する事
によって粘稠な液状重合体１５ｇを得た。Example 1 Tetraphenylporphyrin 0.12 g (0.2 mmol) and diethylaluminum chloride 0.024 g (0.2 m) were placed in a pressure-resistant glass autoclave having a capacity of 100 ml.
mol) and 5 ml of methylene chloride were added and the mixture was reacted for 3 hours with stirring, and then vacuum dried at 50 ° C. for 3 hours to remove unreacted diethylaluminum chloride. Next, while the container was cooled with dry ice-methanol, 17 g of hexafluoropropylene oxide and 6 g of propylene oxide were introduced, the mixture was stirred for 1 hour, the temperature was raised to 0 ° C., and the mixture was reacted for 16 hours under ice cooling. After the reaction, the container was returned to room temperature and the unreacted raw materials were distilled off by an evaporator to obtain 15 g of a viscous liquid polymer.
【００２１】続いてポルフィリンアルミニウム錯体を濾
過分離し、得られた重合体のＩＲにおいて、プロピレン
オキシドのメチル基由来のＣ−Ｈ伸縮振動に基づく吸収
が３０００ｃｍ-1、ヘキサフルオロプロピレンオキシド
のトリフルオロメチル基由来のＣ−Ｆ伸縮振動に基づく
吸収が１４００〜１０００ｃｍ-1、重合末端基の酸フル
オライド由来のＣ＝Ｏ伸縮振動に基づく吸収が１７８０
ｃｍ-1が観察され、原料エポキシ基に由来する吸収は消
失していた。Subsequently, the porphyrin aluminum complex was separated by filtration, and in the IR of the obtained polymer, absorption based on C—H stretching vibration derived from the methyl group of propylene oxide was 3000 cm −1 , and trifluoromethyl hexafluoropropylene oxide. Absorption based on C—F stretching vibration derived from the group is 1400 to 1000 cm −1 , and absorption based on C═O stretching vibration derived from acid fluoride of the polymerization end group is 1780.
cm −1 was observed, and the absorption derived from the raw material epoxy group had disappeared.
【００２２】元素分析の結果、Ｃ；３１．９％，Ｈ；
２．６％，Ｆ；５１．４％であり、重合体には、ヘキサ
フルオロプロピレンオキシドとプロピレンオキシドがほ
ぼ１：１で導入されていた。重合体の分子量はＧＰＣ測
定により、数平均分子量６０００、分子量分布（Ｍｗ／
Ｍｎ）１．２８であった。As a result of elemental analysis, C: 31.9%, H:
2.6%, F; 51.4%, and hexafluoropropylene oxide and propylene oxide were introduced into the polymer at an approximate ratio of 1: 1. The molecular weight of the polymer was determined by GPC to have a number average molecular weight of 6000 and a molecular weight distribution (Mw /
Mn) was 1.28.
【００２３】実施例２〜４ テトラフェニルポルフィリンの代わりに表１に示したポ
ルフィリン化合物を、ジエチルアルミニウムクロリドの
代わりに表１に示した有機金属化合物を用いた以外は実
施例１と同様な方法で反応を行った。その結果、いづれ
の場合も実施例１と同様なＩＲスペクトルが観察され、
原料エポキシ基に由来する吸収は消失していた。元素分
析結果も実施例１と殆んど同じであった。重合体の分子
量および分子量分布は表１に示した。Examples 2 to 4 In the same manner as in Example 1 except that the porphyrin compounds shown in Table 1 were used in place of tetraphenylporphyrin and the organometallic compounds shown in Table 1 were used in place of diethylaluminum chloride. The reaction was carried out. As a result, an IR spectrum similar to that of Example 1 was observed in each case,
The absorption derived from the raw material epoxy group has disappeared. The elemental analysis results were almost the same as in Example 1. The molecular weight and molecular weight distribution of the polymer are shown in Table 1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】比較例１ １００ｍｌ容量の耐圧製ガラスオートクレーブをドライ
アイス−メタノールで冷却した状態で、ヘキサフルオロ
プロピレンオキシド１７ｇ、プロピレンオキシド６ｇを
導入し、１時間攪拌後０℃まで温度を上昇させ氷冷下１
６時間反応させた後、容器を室温に戻し未反応物を分離
して透明な液体を５ｇ得た。得られた重合体は実施例１
と同様なＩＲスペクトルと元素分析結果を示したが、Ｇ
ＰＣによる分子量測定では数平均分子量が８００と低い
値であった。Comparative Example 1 17 g of hexafluoropropylene oxide and 6 g of propylene oxide were introduced in a state where a pressure-resistant glass autoclave having a capacity of 100 ml was cooled with dry ice-methanol, and after stirring for 1 hour, the temperature was raised to 0 ° C. and ice-cooled. Bottom 1
After reacting for 6 hours, the container was returned to room temperature and unreacted substances were separated to obtain 5 g of a transparent liquid. The polymer obtained is described in Example 1.
The same IR spectrum and elemental analysis results were shown as
The number average molecular weight was as low as 800 in the molecular weight measurement by PC.
【００２６】比較例２ １００ｍｌ容量の耐圧製ガラスオートクレーブを用いテ
トラフェニルポルフィリンとジエチルアルミニウムクロ
リドを実施例１と同様に反応させ真空乾燥させた。次に
容器をドライアイス−メタノールで冷却した状態でヘキ
サプロピレンオキサイド１７ｇのみを導入し、実施例１
と同様に反応させたところ全く反応が進行しなかった。Comparative Example 2 Tetraphenylporphyrin and diethylaluminum chloride were reacted in the same manner as in Example 1 using a pressure-resistant glass autoclave having a capacity of 100 ml and vacuum dried. Then, while the container was cooled with dry ice-methanol, only 17 g of hexapropylene oxide was introduced, and Example 1 was used.
When reacted in the same manner as above, the reaction did not proceed at all.
【００２７】実施例５〜６ 実施例１において、ヘキサフルオロプロピレンオキシド
の量だけを３４ｇ，５０ｇの２通りに換えたこと以外は
同様な方法で重合を行なったところ、収量は各々１６．
２ｇと１５．５ｇであった。得られた重合体のＩＲおよ
び元素分析結果は実施例１とほぼ等しく、重合体の分子
量はいずれも数平均分子量６２００、分子量分布（Ｍｗ
／Ｍｎ）は１．３３であった。また、ヘキサフルオロプ
ロピレンオキシドとプロピレンオキシドに基づく繰返し
単位の割合はほぼ１：１であった。Examples 5 to 6 Polymerization was carried out in the same manner as in Example 1 except that only the amount of hexafluoropropylene oxide was changed to 34 g and 50 g, and the yields were 16.
It was 2g and 15.5g. The IR and elemental analysis results of the obtained polymer were almost the same as in Example 1, and the molecular weights of all the polymers were number average molecular weight 6200 and molecular weight distribution (Mw
/ Mn) was 1.33. The ratio of hexafluoropropylene oxide to propylene oxide-based repeating units was about 1: 1.
Claims (1)
ルオロアルキレンオキシドとアルキレンオキシドを共重
合させることを特徴とする含フッ素アルキルポリエーテ
ル重合体の製造方法。1. A method for producing a fluorine-containing alkyl polyether polymer, which comprises copolymerizing perfluoroalkylene oxide and alkylene oxide in the presence of a porphyrin metal complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30012993A JPH07149889A (en) | 1993-11-30 | 1993-11-30 | Production of fluorine-containing alkyl polyether polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30012993A JPH07149889A (en) | 1993-11-30 | 1993-11-30 | Production of fluorine-containing alkyl polyether polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07149889A true JPH07149889A (en) | 1995-06-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30012993A Pending JPH07149889A (en) | 1993-11-30 | 1993-11-30 | Production of fluorine-containing alkyl polyether polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07149889A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6034207A (en) * | 1998-04-01 | 2000-03-07 | Shin-Etsu Chemical Co., Ltd. | Polymers of hexafluoropropene oxide and process of making |
| US6127517A (en) * | 1998-04-01 | 2000-10-03 | Shin-Etsu Chemical Co., Ltd. | Polymerization of hexafluoropropene oxide |
-
1993
- 1993-11-30 JP JP30012993A patent/JPH07149889A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6034207A (en) * | 1998-04-01 | 2000-03-07 | Shin-Etsu Chemical Co., Ltd. | Polymers of hexafluoropropene oxide and process of making |
| US6127517A (en) * | 1998-04-01 | 2000-10-03 | Shin-Etsu Chemical Co., Ltd. | Polymerization of hexafluoropropene oxide |
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