JP2012162693A - Fluorine-containing ion liquid type synthetic lubricating oil - Google Patents
Fluorine-containing ion liquid type synthetic lubricating oil Download PDFInfo
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本発明は、従来のイオン液体型潤滑油よりも高い耐熱性と、高い潤滑性能を有する含フッ素イオン液体型潤滑油に関する。 The present invention relates to a fluorine-containing ionic liquid type lubricating oil having higher heat resistance and higher lubricating performance than conventional ionic liquid type lubricating oils.
従来、機械装置、動力伝達装置、モーター、グリースなどに用いられる潤滑油としてはシリコーンオイル、合成炭化水素、エステル油などの中から所望の物性に近い基油を選定し、あるいは必要に応じて組み合わせて使用されている。場合によってはその他の成分を添加することで要求性能を満たす潤滑油組成物として使用されている。これらの潤滑油基油には、高温での使用の際には、基油自身の安定性、引火や燃焼の懸念があった。設備や装置の進歩に伴い、潤滑油には過酷な状態での使用に対して信頼性の向上が要求されており、より優れた耐熱性、耐酸化性、潤滑性を有する潤滑油基油が求められている。このような問題に対して、イオン液体を含有することを特徴とする合成潤滑油を用いる方法が知られている。（特許文献１、２） Conventionally, base oils close to the desired physical properties are selected from silicone oil, synthetic hydrocarbon, ester oil, etc. as lubricating oils used for mechanical devices, power transmission devices, motors, greases, etc., or combined as necessary Have been used. In some cases, it is used as a lubricating oil composition that satisfies the required performance by adding other components. When these lubricating base oils are used at high temperatures, there are concerns about the stability of the base oil itself, ignition and combustion. With the progress of facilities and equipment, there has been a demand for improved reliability of lubricants for use in harsh conditions. Lubricant base oils with superior heat resistance, oxidation resistance, and lubricity are required. It has been demanded. In order to solve such a problem, a method using a synthetic lubricating oil characterized by containing an ionic liquid is known. (Patent Documents 1 and 2)
イオン液体は塩でありながら、常温で液体であり、且つ蒸気圧が極めて低い、難燃性である等の特徴から、様々な分野で応用が検討されている物質である。高い耐熱性、高い比熱容量などの特徴を活かし、潤滑剤の分野でも応用検討が積極的になされている。しかし、従来のイオン液体の中には、吸湿性を示すものや、場合によっては水に対して溶解性を示すものもあり、潤滑油として用いる場合、その用途によっては適さない可能性があった。また、前述のように、設備や装置の高性能化や高効率化に伴い、潤滑油の、より一層の信頼性の向上が恒常的に望まれており、長期間の使用における揮発損失や熱分解の問題の改善や従来よりも高い潤滑性能を有する潤滑油基油の開発が課題であった。 Although the ionic liquid is a salt, the ionic liquid is a liquid at room temperature, has a very low vapor pressure, and is flame retardant. Taking advantage of features such as high heat resistance and high specific heat capacity, application studies are also being actively conducted in the field of lubricants. However, some of the conventional ionic liquids exhibit hygroscopicity, and in some cases, exhibit solubility in water. When used as a lubricating oil, there is a possibility that it may not be suitable depending on the application. . In addition, as described above, with the improvement in performance and efficiency of facilities and equipment, further improvement in the reliability of lubricating oil is constantly desired. Improvements in decomposition problems and development of lubricating base oils with higher lubrication performance than before were problems.
すなわち本発明は、前述の潤滑剤用途でイオン液体を活用する際の問題点を解決し、従来のものよりも、高い耐熱性と潤滑性を有するイオン液体型潤滑油基油を提供することを目的とする。 That is, the present invention provides an ionic liquid-type lubricating base oil having higher heat resistance and lubricity than the conventional ones by solving the problems in utilizing the ionic liquid in the aforementioned lubricant application. Objective.
本発明者らは、鋭意検討を重ねた結果、従来より潤滑剤への適用が検討されていたイオン液体において、フッ素基を導入したカチオンを用いることにより、従来のイオン液体型潤滑油よりも耐熱性、潤滑特性を向上させることが出来ることを見出した。すなわち、本発明は下記項1〜５の含フッ素イオン液体型潤滑油及び潤滑油組成物を提供するものである。
項１．
イオン液体から構成される含フッ素イオン液体型潤滑油であって、前記イオン液体が下記式（１）
As a result of intensive studies, the present inventors have used a cation introduced with a fluorine group in an ionic liquid that has been studied for application to a lubricant. And improved lubrication characteristics. That is, this invention provides the fluorine-containing ionic liquid type | mold lubricating oil and lubricating oil composition of the following items 1-5.
Item 1.
A fluorine-containing ionic liquid type lubricating oil composed of an ionic liquid, wherein the ionic liquid has the following formula (1)
（式中、Ｒｆはポリフルオロアルキル基、ポリフルオロポリエーテル基を示す。Ａは単結合もしくは２価の有機基を示し、有機基は必要に応じて酸素原子、窒素原子または硫黄原子を含んでもよい。Q+は有機カチオンを表し、X−は分子内にフッ素原子を有するアニオンを表す。）
で表されることを特徴とする、含フッ素イオン液体型潤滑油
項２．
Ｒｆが下記式（２）
(In the formula, Rf represents a polyfluoroalkyl group or a polyfluoropolyether group. A represents a single bond or a divalent organic group, and the organic group may contain an oxygen atom, a nitrogen atom or a sulfur atom as required. Q + represents an organic cation, and X − represents an anion having a fluorine atom in the molecule.
Fluorine-containing ionic liquid type lubricating oil characterized by the following:
Rf is the following formula (2)
（式中nは０〜７の整数を表す）
で表される炭素数１〜８の直鎖状のペルフルオロアルキル基であることを特徴とする、項１に記載の含フッ素イオン液体型潤滑油。
項３．
イオン液体を構成するカチオンが下記式（３）
(Wherein n represents an integer of 0 to 7)
Item 2. The fluorine-containing ionic liquid type lubricating oil according to Item 1, which is a linear perfluoroalkyl group having 1 to 8 carbon atoms represented by:
Item 3.
The cation constituting the ionic liquid is represented by the following formula (3)
（式中、Ｒ１及び／又はＲ３は下記一般式（４）で表される基である。 (In the formula, R 1 and / or R 3 is a group represented by the following general formula (4).
（式中Ｒｆはポリフルオロアルキル基、ポリフルオロポリエーテル基を示す。Ａは単結合もしくは２価の有機基を示し、有機基は必要に応じて酸素原子、窒素原子または硫黄原子を含んでもよい。）。
置換基Ｒ１〜Ｒ５の残りの基は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜１８の直鎖または分岐のアルキル基、アルケニル基、アルキニル基、アルコキシ基、アシル基を示し、これらの置換基は必要に応じて酸素、窒素、硫黄を含んでもよい。）
で表されるイミダゾリウムカチオンであることを特徴とする項１又は２に記載の含フッ素イオン液体型潤滑油。
項４．
分子内にフッ素原子を有する前記アニオンがビス（トリフルオロメタンスルホニル）イミドアニオンであることを特徴とする請求項１〜３のいずれかに記載の含フッ素イオン液体型潤滑油。
項５．
項１〜４のいずれかに記載の含フッ素イオン液体型潤滑油を含むことを特徴とする潤滑油組成物。
(In the formula, Rf represents a polyfluoroalkyl group or a polyfluoropolyether group. A represents a single bond or a divalent organic group, and the organic group may contain an oxygen atom, a nitrogen atom or a sulfur atom if necessary. .)
The remaining groups of the substituents R 1 to R 5 are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, or an acyl group. These substituents may include oxygen, nitrogen and sulfur as required. )
Item 3. The fluorine-containing ionic liquid type lubricating oil according to Item 1 or 2, which is an imidazolium cation represented by the formula:
Item 4.
The fluorine-containing ionic liquid type lubricating oil according to any one of claims 1 to 3, wherein the anion having a fluorine atom in the molecule is a bis (trifluoromethanesulfonyl) imide anion.
Item 5.
Item 5. A lubricating oil composition comprising the fluorine-containing ionic liquid type lubricating oil according to any one of Items 1 to 4.
本発明の含フッ素イオン液体型潤滑油は、イオン液体の有機カチオン部分にポリフルオロアルキル基またはポリフルオロポリエーテル基を有しており、同一炭素数の炭化水素基を有するイオン液体と比較した場合、耐熱性、摩擦特性に関して優れている。耐熱性や摩擦特性は、設備や装置の高性能化や高効率化に伴って潤滑油に求められるている性能であり、本発明の成果は、より優れた耐熱性や摩擦特性を有する潤滑油および潤滑油基油として利用が出来る。 The fluorine-containing ionic liquid type lubricating oil of the present invention has a polyfluoroalkyl group or a polyfluoropolyether group in the organic cation portion of the ionic liquid, and is compared with an ionic liquid having a hydrocarbon group having the same carbon number Excellent in heat resistance and friction characteristics. Heat resistance and friction characteristics are performances required for lubricating oils as equipment and equipment become more sophisticated and more efficient, and the results of the present invention are lubricating oils with superior heat resistance and friction characteristics. It can be used as a lubricating base oil.
以下、本発明の含フッ素イオン液体型潤滑油について詳述する。 Hereinafter, the fluorine-containing ionic liquid type lubricating oil of the present invention will be described in detail.
本発明の含フッ素イオン液体型潤滑油は下記一般式（１） The fluorine-containing ionic liquid type lubricating oil of the present invention has the following general formula (1)
（式中、Ｒｆはポリフルオロアルキル基、ポリフルオロポリエーテル基を示す。Ａは単結合もしくは２価の有機基を示し、有機基は必要に応じて酸素原子や窒素原子や硫黄原子を含んでもよい。Q+は有機カチオンを表し、X−は分子内にフッ素原子を有するアニオンを表す。）
で表されることを特徴とする。
(In the formula, Rf represents a polyfluoroalkyl group or a polyfluoropolyether group. A represents a single bond or a divalent organic group, and the organic group may contain an oxygen atom, a nitrogen atom, or a sulfur atom as necessary. Q + represents an organic cation, and X − represents an anion having a fluorine atom in the molecule.
It is represented by.
一般式（１）において、Ｒｆはポリフルオロアルキル基、ポリフルオロポリエーテル基を示す。ポリフルオロアルキル基の炭素数は、１〜１０、好ましくは２〜９、より好ましくは４〜８であり、直鎖であっても分岐を有していてもよい。Ｒｆは直鎖のポリフルオロアルキル基が好ましい。ポリフルオロアルキル基は、アルキル基の少なくとも２個の水素原子がフッ素原子で置換された基を意味し、フッ素置換基の数は特に限定されないが全ての水素原子がフッ素原子で置換されたペルフルオロアルキル基が好ましい。Ｒｆとしては具体的に、炭素数１〜８の直鎖状ペルフルオロアルキル基、炭素数３〜９の分岐状ペルフルオロアルケニル基、平均分子量１０００以下のペルフルオロポリエーテル基などが挙げられる。
ペルフルオロポリエーテル基としては、
CF3-CF2-CF2-O-[CF(CF3)-CF2-O]n-CF(CF3)-
CF3-CF2-CF2-O-(CF2-CF2-CF2-O)n-CF2-CF2-
CF3-O-(CF2-CF2-O)m-(CF2-O-)n-CF2-
（ｎ，ｍは、ペルフルオロポリエーテル基の平均分子量が１０００以下になる０以上の整数を表す。）が挙げられる。
In the general formula (1), Rf represents a polyfluoroalkyl group or a polyfluoropolyether group. The polyfluoroalkyl group has 1 to 10 carbon atoms, preferably 2 to 9 carbon atoms, more preferably 4 to 8 carbon atoms, and may be linear or branched. Rf is preferably a linear polyfluoroalkyl group. The polyfluoroalkyl group means a group in which at least two hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the number of fluorine substituents is not particularly limited, but is a perfluoroalkyl in which all hydrogen atoms are substituted with fluorine atoms. Groups are preferred. Specific examples of Rf include a linear perfluoroalkyl group having 1 to 8 carbon atoms, a branched perfluoroalkenyl group having 3 to 9 carbon atoms, and a perfluoropolyether group having an average molecular weight of 1000 or less.
As perfluoropolyether group,
CF3-CF2-CF2-O- [CF (CF3) -CF2-O] n-CF (CF3)-
CF3-CF2-CF2-O- (CF2-CF2-CF2-O) n-CF2-CF2-
CF3-O- (CF2-CF2-O) m- (CF2-O-) n-CF2-
(N and m represent an integer of 0 or more at which the average molecular weight of the perfluoropolyether group is 1000 or less.).
好ましいＲｆとしては炭素数１〜８の直鎖状ペルフルオロアルキル基が挙げられる。このようなペルフルオロアルキル基としては、特に限定されないが、たとえば下記一般式（２）で表されるペルフルオロアルキル基が挙げられる。 Preferable Rf includes a linear perfluoroalkyl group having 1 to 8 carbon atoms. Although it does not specifically limit as such a perfluoroalkyl group, For example, the perfluoroalkyl group represented by following General formula (2) is mentioned.
（式中nは０〜７の整数を表す）
一般式（１）において、Aは単結合もしくは2価の有機基を示す。2価の有機基としては、具体的に、炭素数１〜４、好ましくは１〜２のアルキレン基が挙げられ、必要に応じて、
酸素原子、窒素原子、硫黄原子を含んでもよい。具体的には、−ＣＨ２−、−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ（ＣＨ３）−、−ＣＨ２ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＣＨ２ＣＨ２−、−ＯＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２Ｏ−、−ＯＣＨ２ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＣＨ２Ｏ−、−ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ−、−ＳＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２Ｓ−、−ＳＣＨ２ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＣＨ２Ｓ−、−ＳＣＨ２ＣＨ２ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｓ−、−ＮＨＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＮＨ−、−ＮＨＣＨ２ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＣＨ２ＮＨ−、−ＮＨＣＨ２ＣＨ２ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＮＨ−などが挙げられる。
(Wherein n represents an integer of 0 to 7)
In the general formula (1), A represents a single bond or a divalent organic group. Specific examples of the divalent organic group include an alkylene group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.
An oxygen atom, a nitrogen atom, and a sulfur atom may be included. Specifically, -CH 2 -, - CH 2 CH 2 -, - CH 2 CH (CH 3) -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - OCH 2 CH 2 -, - CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 O—, —SCH 2 CH 2 —, —CH 2 CH 2 S—, —SCH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 S—, —SCH 2 CH 2 CH 2 CH 2 —, — CH 2 CH 2 CH 2 CH 2 S -, - NHCH 2 CH 2 -, - CH 2 CH 2 NH -, - NHCH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 NH -, - NHCH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 NH- and the like.
好ましいAとしては、工業的な原料の入手の容易さの点からも、炭素数１〜２のアルキレン基が好ましい。 As preferred A, an alkylene group having 1 to 2 carbon atoms is preferred from the viewpoint of easy availability of industrial raw materials.
一般式（１）においてQ+ は有機カチオンを表す。有機カチオンとしては具体的に、脂肪族アンモニウムカチオン、飽和環式アンモニウムカチオン、芳香族アンモニウムカチオン、第四級ホスホニウムカチオンが示される。好ましい有機カチオンとしては、イミダゾリウムカチオンやピリジニウムカチオン等の芳香族アンモニウムカチオンが挙げられ、特に好ましい有機カチオンとしてはイミダゾリウムカチオンが挙げられる。イオン液体のカチオン（Ｒｆ−Ａ−Ｑ＋）は下記式（３）のイミダゾリウムカチオンが好ましい。 In the general formula (1), Q + represents an organic cation. Specific examples of the organic cation include an aliphatic ammonium cation, a saturated cyclic ammonium cation, an aromatic ammonium cation, and a quaternary phosphonium cation. Preferable organic cations include aromatic ammonium cations such as imidazolium cations and pyridinium cations, and particularly preferable organic cations include imidazolium cations. The cation (Rf-AQ + ) of the ionic liquid is preferably an imidazolium cation of the following formula (3).
（式中、Ｒ１及び／又はＲ３は下記一般式（４）で表される基である。 (In the formula, R 1 and / or R 3 is a group represented by the following general formula (4).
（式中Ｒｆ、Ａは一般式（１）におけるＲｆ、Ａと同義である）。 (Wherein Rf and A have the same meanings as Rf and A in formula (1)).
置換基Ｒ１〜Ｒ５の残りの基は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜１８の直鎖または分岐のアルキル基、アルケニル基、アルキニル基、アルコキシ基、アシル基を示し、これらの置換基は必要に応じて酸素、窒素、硫黄を含んでもよい。） The remaining groups of the substituents R 1 to R 5 are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, or an acyl group. These substituents may include oxygen, nitrogen and sulfur as required. )
上記式（３）で表されるイミダゾリウムカチオンは合成の容易さの観点から１，３位の２置換イミダゾリウムカチオン、１，２，３位の３置換イミダゾリウムカチオンが好ましく用いられる。１，２，３位の置換基、好ましくは１，３位の置換基のうち、少なくとも一つがポリフルオロアルキル基またはポリフルオロポリエーテル基であることが好ましい。 As the imidazolium cation represented by the above formula (3), a 1,3-positioned 2-substituted imidazolium cation and a 1,2,3-positioned 3-substituted imidazolium cation are preferably used from the viewpoint of ease of synthesis. It is preferable that at least one of the substituents at the 1,2,3 position, preferably the 1,3 position is a polyfluoroalkyl group or a polyfluoropolyether group.
一般式（１）においてX−は分子内にフッ素原子を有するアニオンを表す。分子内にフッ素原子を有するアニオンとしては、具体的にペルフルオロアルカンスルホネートアニオン（Ｒｆ１−ＳＯ３ −）、やビス（パーフルオロアルカンスルホニル）イミドアニオン（｛Ｒｆ１−ＳＯ２｝２Ｎ−）、ビス（フルオロスルホニル）イミドアニオン（｛Ｆ−ＳＯ２｝２Ｎ−）、六フッ化リンアニオン（ＰＦ６）、四フッ化ホウ素アニオン（ＢＦ４）などの含フッ素アニオンが挙げられる。Ｒｆ１は炭素数１〜１０の直鎖又は分岐を有するペルフルオロアルキル基が挙げられ、具体的にはＣＦ３−（ＣＦ２）ｍ−（ｍは０〜９の整数を示す）で表される基が挙げられる。 In the general formula (1), X − represents an anion having a fluorine atom in the molecule. As an anion having a fluorine atom in the molecule, specifically, a perfluoroalkanesulfonate anion (Rf 1 —SO 3 − ), a bis (perfluoroalkanesulfonyl) imide anion ({Rf 1 —SO 2 } 2 N − ), Fluorine-containing anions such as bis (fluorosulfonyl) imide anion ({F—SO 2 } 2 N − ), phosphorus hexafluoride anion (PF 6 ), and boron tetrafluoride anion (BF 4 ) can be mentioned. Rf 1 includes a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, and is specifically represented by CF 3- (CF 2 ) m- (m represents an integer of 0 to 9). Groups.
好ましいアニオンとしては、ビス（パーフルオロアルカンスルホニル）イミドアニオン挙げられ、特に好ましいアニオンとしてはビス（トリフルオロメタンスルホニル）イミドアニオンが挙げられる。 Preferred anions include bis (perfluoroalkanesulfonyl) imide anions, and particularly preferred anions include bis (trifluoromethanesulfonyl) imide anions.
本発明におけるイオン液体の合成方法としては、特に限定されるものではなく、従来公知の方法を用いて製造することが出来る。例えば、一般的なアルキル化反応やアニオン交換反応などを適用することが出来る。 The method for synthesizing the ionic liquid in the present invention is not particularly limited, and can be produced using a conventionally known method. For example, a general alkylation reaction or anion exchange reaction can be applied.
イオン液体において、カチオン、アニオンは、１種のみを用いてもよく、２種以上のカチオン／アニオンを混合して用いてもよい。 In the ionic liquid, only one kind of cation and anion may be used, or two or more kinds of cation / anion may be mixed and used.
本発明の内容を以下の実施例により説明するが、本発明の内容は実施例に限定されることは意図しない。 The contents of the present invention will be described by the following examples, but the contents of the present invention are not intended to be limited to the examples.
合成実施例１
攪拌機、温度計、還流冷却機及び滴下漏斗を備えたフラスコにＨＦＥ−７１００（住友３Ｍ製）３０ｍｌ、ピリジン０．９５ｇ（０．０１２ｍｏｌ）及び１H，１H，２H，２H−トリデカフルオロ−１−ｎ−オクタノール（東京化成、試薬）３．６４ｇ（０．０１ｍｏｌ）を０℃で攪拌しながら、トリフルオロメタンスルホン酸無水物（東京化成、試薬）３３．８６ｇ（０．１２ｍｏｌ）を除々に滴下し、更に攪拌を３〜４時間実施した後、反応混合物を水１００ｍｌ中に滴下した。
Synthesis Example 1
In a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 30 ml of HFE-7100 (manufactured by Sumitomo 3M), 0.95 g (0.012 mol) of pyridine and 1H, 1H, 2H, 2H-tridecafluoro-1- While stirring 3.64 g (0.01 mol) of n-octanol (Tokyo Kasei, reagent) at 0 ° C., 33.86 g (0.12 mol) of trifluoromethanesulfonic acid anhydride (Tokyo Kasei, reagent) was gradually added dropwise. After further stirring for 3 to 4 hours, the reaction mixture was dropped into 100 ml of water.
分離した下層を２〜３回水洗し、無水硫酸ナトリウムで脱水後、ロータリーエバポレーターを用いて、ＨＦＥ−７１００を留去することで、淡黄色液体である１H，１H，２H，２H−トリデカフルオロオクチル−１−トリフルオロメタンスルホネートを４．４７ｇ（９ｍｍｏｌ、収率９０％）得た。 The separated lower layer was washed 2 to 3 times with water, dehydrated with anhydrous sodium sulfate, and then HFE-7100 was distilled off using a rotary evaporator, whereby 1H, 1H, 2H, 2H-tridecafluoro, which is a pale yellow liquid, was removed. 4.47 g (9 mmol, yield 90%) of octyl-1-trifluoromethanesulfonate was obtained.
攪拌機、温度計、還流冷却機及び滴下漏斗を備えたフラスコに１−メチルイミダゾール（東京化成、試薬）０．８９ｇ（１０．８ｍｍｏｌ）、アセトニトリル３０ｍｌを４０〜５０℃に加温し、攪拌しながら、合成した１H，１H，２H，２H−トリデカフルオロオクチル−１−トリフルオロメタンスルホネート４．４７ｇ（９ｍｍｏｌ）を滴下した。更に４０〜５０℃で３〜４時間攪拌を継続させ、反応混合物を水５０ｍｌ中に滴下した。分離した下層を５〜１０回蒸留水洗し、１−メチル−３−（１H，１H，２H，２H−トリデカフルオロ−ｎ−オクチル）イミダゾリウム・トリフルオロメタンスルホネート、４．７４ｇ（８．２ｍｍｏｌ、収率９１％）を得た。 In a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel, 0.89 g (10.8 mmol) of 1-methylimidazole (Tokyo Kasei, reagent) and 30 ml of acetonitrile were heated to 40 to 50 ° C. while stirring. Then, 4.47 g (9 mmol) of synthesized 1H, 1H, 2H, 2H-tridecafluorooctyl-1-trifluoromethanesulfonate was added dropwise. Further, stirring was continued at 40 to 50 ° C. for 3 to 4 hours, and the reaction mixture was dropped into 50 ml of water. The separated lower layer was washed 5 to 10 times with distilled water, and 1-methyl-3- (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) imidazolium trifluoromethanesulfonate, 4.74 g (8.2 mmol, Yield 91%) was obtained.
合成実施例２
次いで、１−メチル−３−（１H，１H，２H，２H−トリデカフルオロ−ｎ−オクチル）イミダゾリウム・トリフルオロメタンスルホネート、４．７４ｇ（８．２ｍｍｏｌ）をメタノール溶媒中、室温にてビス(トリフルオロメタンスルホニル)イミドリチウム、２．４７ｇ（８．６ｍｍｏｌ）と塩交換反応させ、得られた反応液を蒸留水で５〜１０回水洗し、その後、分離した下層から水分を減圧除去することによって、目的物である１−メチル−３−（１H，１H，２H，２H−トリデカフルオロ−ｎ−オクチル）イミダゾリウム・ビス(トリフルオロメタンスルホニル)イミド、５．２８ｇ（７．４ｍｍｏｌ、収率９０％）を得た。
Synthesis Example 2
Subsequently, 1-methyl-3- (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) imidazolium trifluoromethanesulfonate, 4.74 g (8.2 mmol) was bis (( By subjecting it to salt exchange reaction with 2.47 g (8.6 mmol) of trifluoromethanesulfonyl) imide lithium, washing the resulting reaction solution with distilled water 5 to 10 times, and then removing the water from the separated lower layer under reduced pressure. 1-methyl-3- (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) imidazolium bis (trifluoromethanesulfonyl) imide, 5.28 g (7.4 mmol, yield 90) %).
合成比較例１
合成実施例１に示した、１H，１H，２H，２H−トリデカフルオロ−１−ｎ−オクタノールの代わりにｎ−オクタノールを用いる以外は合成実施例１と同様にして、１−メチル−３−ｎ−オクチルイミダゾリウム・トリフルオロメタンスルホネートを収率９１％で得た。その後、合成実施例２と同様にして、１−メチル−３−ｎ−オクチルイミダゾリウム・ビス(トリフルオロメタンスルホニル)イミドを収率９０％で得た。
Synthesis Comparative Example 1
In the same manner as in Synthesis Example 1 except that n-octanol was used in place of 1H, 1H, 2H, 2H-tridecafluoro-1-n-octanol shown in Synthesis Example 1, 1-methyl-3- n-Octylimidazolium trifluoromethanesulfonate was obtained in a yield of 91%. Thereafter, in the same manner as in Synthesis Example 2, 1-methyl-3-n-octylimidazolium bis (trifluoromethanesulfonyl) imide was obtained in a yield of 90%.
合成比較例２
合成実施例１において、１−メチル−３−（１H，１H，２H，２H―トリデカフルオロ−ｎ−オクチル）イミダゾリウム・トリフルオロメタンスルホネートの代わりに、１−ブチル−３−メチルイミダゾリウム・クロライドを用いる以外は同様にして、１−ブチル−３−メチルイミダゾリウム・ビス(トリフルオロメタンスルホニル)イミドを収率９１％で得た。
Synthesis Comparative Example 2
In Synthesis Example 1, instead of 1-methyl-3- (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) imidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium chloride 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide was obtained in a similar manner except that was used.
実施例１
合成実施例２で合成した、１−メチル−３−（１H，１H，２H，２H―トリデカフルオロ−ｎ−オクチル）イミダゾリウム・ビス(トリフルオロメタンスルホニル)イミドを用いて、摩擦係数測定、耐熱性測定、融点測定、粘度測定を行い、潤滑油基油としての性能を評価した。
Example 1
Using 1-methyl-3- (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) imidazolium bis (trifluoromethanesulfonyl) imide synthesized in Synthesis Example 2, friction coefficient measurement, heat resistance The performance as a lubricating base oil was evaluated by measuring the property, melting point and viscosity.
摩擦係数測定は新東科学社製 ＨＥＩＤＯＮ−１４ＤＲＨ広域摩擦磨耗試験機を用い、測定温度２０℃、荷重２００ｇで、５０ｒｐｍと１００ｒｐｍの２条件にて測定を行った。測定基材としてはアルミニウムを用いた。 The friction coefficient was measured using a HEIDON-14DRH wide-area frictional wear tester manufactured by Shinto Kagaku Co., Ltd. at a measurement temperature of 20 ° C. and a load of 200 g under two conditions of 50 rpm and 100 rpm. Aluminum was used as the measurement substrate.
耐熱性測定はエスアイアイナノテクノロジー社製 ＴＧ／ＤＴＡ６２００を用いて、１５０ｍｌ／分の空気気流下、１０℃／分の昇温速度にて、５％重量減少温度を測定することで評価した。 The heat resistance measurement was evaluated by measuring a 5% weight loss temperature using a TG / DTA6200 manufactured by SII Nano Technology Co., Ltd. under an air stream of 150 ml / min at a heating rate of 10 ° C./min.
融点はエスアイアイナノテクノロジー社製 ＤＳＣ６２００を用いて、１０℃／分の速度で室温から−６０℃までの測定により評価した。 The melting point was evaluated by measuring from room temperature to −60 ° C. at a rate of 10 ° C./min using DSC6200 manufactured by SII Nano Technology.
粘度測定は、ブルックフィールド社製 DV−ｕｌｔｒａを用いて３０℃における粘度測定を実施した。評価結果を表１に示す。 The viscosity was measured at 30 ° C. using DV-ultra manufactured by Brookfield. The evaluation results are shown in Table 1.
比較例１
合成比較例１で合成した、１−メチルー３−ｎ−オクチルイミダゾリウム・ビス(トリフルオロメタンスルホニル)イミドを用いて、実施例１と同様に、摩擦係数測定、耐熱性測定、融点測定、粘度測定を行い、潤滑油基油としての性能を評価した。評価結果を表１に示す。
Comparative Example 1
Using 1-methyl-3-n-octylimidazolium bis (trifluoromethanesulfonyl) imide synthesized in Synthesis Comparative Example 1, friction coefficient measurement, heat resistance measurement, melting point measurement, viscosity measurement in the same manner as in Example 1. The performance as a lubricating base oil was evaluated. The evaluation results are shown in Table 1.
比較例２
合成比較例２で合成した、１−ブチル−３−メチルイミダゾリウム・ビス(トリフルオロメタンスルホニル)イミドを用いて、実施例１と同様に、摩擦係数測定、耐熱性測定、融点測定、粘度測定を行い、潤滑油基油としての性能を評価した。評価結果を表１に示す。
Comparative Example 2
Using 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide synthesized in Synthesis Comparative Example 2, friction coefficient measurement, heat resistance measurement, melting point measurement, and viscosity measurement were performed in the same manner as in Example 1. The performance as a lubricating base oil was evaluated. The evaluation results are shown in Table 1.
表１の結果から、イミダゾリウムカチオンの置換基に直鎖状ペルフルオロアルキル基を導入した場合、同炭素数の炭化水素基が導入されたものよりも耐熱性が優れていることが判る。また、フッ素基の導入により、同炭素数の炭化水素基が導入されたものよりも低い摩擦係数を示す。 From the results in Table 1, it can be seen that when a linear perfluoroalkyl group is introduced into the substituent of the imidazolium cation, the heat resistance is superior to those in which a hydrocarbon group having the same carbon number is introduced. Moreover, the introduction of fluorine groups shows a lower coefficient of friction than that in which hydrocarbon groups having the same carbon number are introduced.
本発明による含フッ素イオン液体型潤滑油は、イオン液体の有機カチオン部分にポリフルオロアルキル基を有しており、同一炭素数の炭化水素基を有するイオン液体と比較した場合、耐熱性、摩擦特性に優れている。耐熱性や摩擦特性は、産業上の設備、装置の高性能化や高効率化に伴って潤滑油に要求される性能であり、本発明の成果は、より優れた耐熱性や摩擦特性を有する潤滑油および潤滑油基油として有用である。 The fluorine-containing ionic liquid type lubricating oil according to the present invention has a polyfluoroalkyl group in the organic cation portion of the ionic liquid, and has heat resistance and friction characteristics when compared with an ionic liquid having a hydrocarbon group having the same carbon number. Is excellent. Heat resistance and friction characteristics are performances required for lubricating oils as industrial equipment and devices become more sophisticated and more efficient, and the results of the present invention have better heat resistance and friction characteristics. Useful as lubricating oil and lubricating base oil.
Claims (5)
で表されることを特徴とする、含フッ素イオン液体型潤滑油。 A fluorine-containing ionic liquid type lubricating oil composed of an ionic liquid, wherein the ionic liquid has the following formula (1)
The fluorine-containing ionic liquid type lubricating oil characterized by these.
で表される炭素数１〜８の直鎖状のペルフルオロアルキル基であることを特徴とする、請求項１に記載の含フッ素イオン液体型潤滑油。 Rf is the following formula (2)
The fluorine-containing ionic liquid type lubricating oil according to claim 1, which is a linear perfluoroalkyl group having 1 to 8 carbon atoms represented by:
置換基Ｒ１〜Ｒ５の残りの基は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜１８の直鎖または分岐のアルキル基、アルケニル基、アルキニル基、アルコキシ基、アシル基を示し、これらの置換基は必要に応じて酸素、窒素、硫黄を含んでもよい。）
で表されるイミダゾリウムカチオンであることを特徴とする請求項１又は２に記載の含フッ素イオン液体型潤滑油。 The cation constituting the ionic liquid is represented by the following formula (3)
The remaining groups of the substituents R 1 to R 5 are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, or an acyl group. These substituents may include oxygen, nitrogen and sulfur as required. )
The fluorine-containing ionic liquid type lubricating oil according to claim 1, wherein the fluorinated ionic liquid type lubricating oil is represented by the formula:
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