JPWO2020129538A1 - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
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- JPWO2020129538A1 JPWO2020129538A1 JP2020515058A JP2020515058A JPWO2020129538A1 JP WO2020129538 A1 JPWO2020129538 A1 JP WO2020129538A1 JP 2020515058 A JP2020515058 A JP 2020515058A JP 2020515058 A JP2020515058 A JP 2020515058A JP WO2020129538 A1 JPWO2020129538 A1 JP WO2020129538A1
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- Japan
- Prior art keywords
- fullerene derivative
- oil composition
- lubricating oil
- group
- perfluoropolyether
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 40
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 35
- 239000003921 oil Substances 0.000 claims abstract description 31
- 239000002199 base oil Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000005461 lubrication Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 241000446313 Lamella Species 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910003472 fullerene Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 229940078499 tricalcium phosphate Drugs 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 description 3
- BZBLUUDREZEDDJ-UHFFFAOYSA-N 2,2,3,3-tetrachloro-1,1,1,4,4,4-hexafluorobutane Chemical compound FC(F)(F)C(Cl)(Cl)C(Cl)(Cl)C(F)(F)F BZBLUUDREZEDDJ-UHFFFAOYSA-N 0.000 description 2
- BTQAJGSMXCDDAJ-UHFFFAOYSA-N 2,4,6-trihydroxybenzaldehyde Chemical compound OC1=CC(O)=C(C=O)C(O)=C1 BTQAJGSMXCDDAJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- GDSIBPPJKSBCMF-UHFFFAOYSA-N 1-(2,4,6-trihydroxyphenyl)ethanone;hydrate Chemical compound O.CC(=O)C1=C(O)C=C(O)C=C1O GDSIBPPJKSBCMF-UHFFFAOYSA-N 0.000 description 1
- WDIFKQOHZPTQIR-UHFFFAOYSA-N 2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-[1,1,2,2-tetrafluoro-2-(1,1,2,2,3,3,4,4,4-nonafluorobutoxy)ethoxy]ethoxy]ethanol Chemical compound OCC(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F WDIFKQOHZPTQIR-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 208000010247 contact dermatitis Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
Abstract
基油としてのパーフルオロポリエーテル油と、パーフルオロポリエーテル鎖を含む基を有するフラーレン誘導体とを有し、前記基油100質量部に対して、前記フラーレン誘導体を0.0001〜0.2000質量部を含有する潤滑油組成物。It has a perfluoropolyether oil as a base oil and a fullerene derivative having a group containing a perfluoropolyether chain, and 0.0001 to 0.2000 mass of the fullerene derivative with respect to 100 parts by mass of the base oil. Lubricating oil composition containing a part.
Description
本発明は、フッ素系潤滑油組成物に関する。 The present invention relates to a fluorine-based lubricating oil composition.
近年、高速化、高効率化、高圧化及び小型化に伴い、自動車、工業機械等に使用される潤滑油には、高圧、高速、高荷重及び高温度下で使用しても長時間にわたって充分に機械寿命を保証できる優れた潤滑性能が要求されている。このような状況下において、優れた熱安定性、低揮発性、耐薬品性、耐樹脂性および温度粘度特性を有する含フッ素系オイル、特にパーフルオロポリエーテル油は、潤滑組成物の基油として、注目を集めている。しかしながら、パーフルオロポリエーテル油は、エステル油や、合成炭化水素油等の合成油と比べて、金属とのなじみが悪く、過酷な条件下では潤滑に十分な油膜を得ることができず、耐摩耗性、耐焼付き性について、一般的な合成油よりも劣っている。また、パーフルオロポリエーテル油は、大部分の一般的な合成油に配合可能な非フッ素系耐摩耗剤、極圧剤等との相溶性が悪く、添加剤の添加による十分な耐摩耗性、耐焼付性を得ることが困難である。 In recent years, with the increase in speed, efficiency, high pressure, and miniaturization, lubricating oils used in automobiles, industrial machines, etc. are sufficient for a long time even when used under high pressure, high speed, high load, and high temperature. Excellent lubrication performance that can guarantee the machine life is required. Under such circumstances, fluorine-containing oils having excellent thermal stability, low volatility, chemical resistance, resin resistance and temperature viscosity characteristics, particularly perfluoropolyether oil, can be used as the base oil of the lubricating composition. , Attracting attention. However, perfluoropolyether oil has poorer compatibility with metals than synthetic oils such as ester oils and synthetic hydrocarbon oils, and under harsh conditions, it is not possible to obtain an oil film sufficient for lubrication, and it is resistant. It is inferior to general synthetic oils in terms of wear resistance and seizure resistance. In addition, perfluoropolyether oil has poor compatibility with non-fluorine-based abrasion resistant agents, extreme pressure agents, etc. that can be blended with most general synthetic oils, and has sufficient abrasion resistance due to the addition of additives. It is difficult to obtain seizure resistance.
特許文献1には、フッ素油と、第三リン酸カルシウムを有する潤滑組成物が開示されている。この文献の方法では、摩擦摩耗特性を改善するために、大量の第三リン酸カルシウムを添加する必要があり、第三リン酸カルシウムの凝集により、潤滑性能の劣化が懸念される。 Patent Document 1 discloses a lubricating composition having a fluorine oil and a tricalcium phosphate. In the method of this document, it is necessary to add a large amount of tricalcium phosphate in order to improve the frictional wear characteristics, and there is a concern that the lubrication performance may be deteriorated due to the aggregation of the tricalcium phosphate.
また、特許文献2において、「パーフルオロポリエーテル基油に、一般式RfRPO(OR')2(ここで、Rfはパーフルオロポリエーテル基であり、Rは炭素数2〜6のアルキレン基であり、R'は水素原子、炭素数1〜6のアルキル基、シクロヘキシル基、ビニル基、フェニル基、トリル基、ベンジル基、フェニルエチル基またはこれらのハロゲン原子置換基である)で表わされる含フッ素有機リン化合物を添加してなる潤滑油組成物」が開示されているが、潤滑特性を更なる改善が望まれる。Further, in Patent Document 2, "a perfluoropolyether base oil has a general formula RfRPO (OR') 2 (where Rf is a perfluoropolyether group and R is an alkylene group having 2 to 6 carbon atoms." , R'is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a vinyl group, a phenyl group, a trill group, a benzyl group, a phenylethyl group or a halogen atom substituent thereof). A "lubricating oil composition to which a phosphorus compound is added" has been disclosed, but further improvement in lubricating properties is desired.
本発明者らは、以上の事情に鑑みてなされたものであり、十分な耐摩耗性を有するフッ素系潤滑油組成物を提供することを課題としている。 The present inventors have made this in view of the above circumstances, and an object of the present invention is to provide a fluorine-based lubricating oil composition having sufficient wear resistance.
本発明は、上記課題を解決するため、以下の[1]〜[5]を含む。
[1]基油としてのパーフルオロポリエーテル油と、パーフルオロポリエーテル鎖を含む基を有するフラーレン誘導体とを有し、前記基油100質量部に対して、前記フラーレン誘導体を0.0001〜0.2000質量部を含有する潤滑油組成物。
[2]10mlあたりの長径1μm以上の固体粒子が1個未満である、前項[1]に記載の潤滑油組成物。
[3]前記フラーレン誘導体におけるパーフルオロポリエーテル鎖を含む基は、アリール基を有する接合構造を介して、フラーレン骨格に接合することを特徴とする前項[1]又は前項[2]に記載の潤滑油組成物。
[4]前記フラーレン誘導体が、下記の式(1)または式(2)で表される構造を有する化合物から選択される少なくとも1種であることを特徴とする前項[1]〜[3]のいずれかに記載の潤滑油組成物。The present invention includes the following [1] to [5] in order to solve the above problems.
[1] It has a perfluoropolyether oil as a base oil and a fullerene derivative having a group containing a perfluoropolyether chain, and the fullerene derivative is 0.0001 to 0 with respect to 100 parts by mass of the base oil. . Lubricating oil composition containing 2000 parts by mass.
[2] The lubricating oil composition according to the preceding item [1], wherein the number of solid particles having a major axis of 1 μm or more per 10 ml is less than one.
[3] The lubrication according to the preceding item [1] or the preceding item [2], wherein the group containing the perfluoropolyether chain in the fullerene derivative is bonded to the fullerene skeleton via a bonding structure having an aryl group. Oil composition.
[4] The above-mentioned items [1] to [3], wherein the fullerene derivative is at least one selected from compounds having a structure represented by the following formula (1) or formula (2). The lubricating oil composition according to any one.
[5]前記R1及びR2は、お互い独立して、炭素数24以下のアルキル基又はアリール基である前項[4]に記載の潤滑油組成物。
[5] The lubricating oil composition according to the preceding item [4], wherein R 1 and R 2 are alkyl groups or aryl groups having 24 or less carbon atoms independently of each other.
本発明によれば、耐摩耗性が優れたフッ素系潤滑油組成物を提供することができる。 According to the present invention, it is possible to provide a fluorine-based lubricating oil composition having excellent wear resistance.
以下、本発明の一実施形態を挙げて、詳細に説明する。なお、本発明はその要旨を変更しない範囲で適宜変更して実施することが可能である。 Hereinafter, an embodiment of the present invention will be described in detail. It should be noted that the present invention can be appropriately modified and implemented without changing the gist thereof.
本実施形態で得られる潤滑油組成物は、パーフルオロポリエーテル油からなる基油と、パーフルオロポリエーテル鎖を含む基を有するフラーレン誘導体を含有し、基油100質量部に対して、フラーレン誘導体の含有量は0.0001〜0.2000質量部である。 The lubricating oil composition obtained in the present embodiment contains a base oil composed of perfluoropolyether oil and a fullerene derivative having a group containing a perfluoropolyether chain, and is a fullerene derivative with respect to 100 parts by mass of the base oil. The content of is 0.0001 to 0.2000 parts by mass.
本実施形態に係るパーフルオロポリエーテル油としては、特に限定されるものではなく、通常公知のものは好適に用いられる。例えば、下記の一般式(i)または(ii)の構造を有するものを用いることが可能である。
(i) Rf1−O(CF2O)e(C2F4O)f〔CF(CF3)CF2O〕g−Rf2(ここで、Rf1、Rf2は、それぞれ独立に炭素数1〜5のパーフルオロアルキル基を表す。なお、e、f、gは0または正の整数であり、かつ、e+f+g=2〜200である)
(ii) F(CF2CF2CF2O)hC2F5
(ここで、hは2〜200の整数を意味する。)
上記のパーフルオロポリエーテル油は、一種類を単独で使用しても良く、またこれらの中から選ばれる2種以上のものを任意の割合で混合して使用してもよい。
(フラーレン誘導体)
本発明の実施形態に係るフラーレン誘導体は、パーフルオロポリエーテル鎖を含む基を有するものである。The perfluoropolyether oil according to the present embodiment is not particularly limited, and generally known oils are preferably used. For example, one having the structure of the following general formula (i) or (ii) can be used.
(I) Rf 1 −O (CF 2 O) e (C 2 F 4 O) f [CF (CF 3 ) CF 2 O] g − Rf 2 (Here, Rf 1 and Rf 2 are independently carbon. Represents a perfluoroalkyl group of the number 1-5. Note that e, f, and g are 0 or a positive integer, and e + f + g = 2 to 200).
(Ii) F (CF 2 CF 2 CF 2 O) h C 2 F 5
(Here, h means an integer of 2 to 200.)
As the above-mentioned perfluoropolyether oil, one kind may be used alone, or two or more kinds selected from these may be mixed and used in an arbitrary ratio.
(Fullerene derivative)
The fullerene derivative according to the embodiment of the present invention has a group containing a perfluoropolyether chain.
本発明の実施形態に係るフラーレン誘導体中のフラーレン骨格としては、例えば、C60、C70、C76、C78、さらに高次のフラーレンが挙げられるが、潤滑油への溶解性の高さの点から、C60及びC70が好ましく、純度の高いものを工業的に容易に得る点と、潤滑油への着色が少ない点から、C60がより好ましい。また、フラーレン誘導体のコストを低減するため、フラーレン誘導体の合成工程において、C60とその他のフラーレンとの混合物であるミックスフラーレンを用いることもできる。ミックスフラーレンを使用する場合、C60の質量割合が全体の50%以上であることが好ましい。Examples of the fullerene skeleton in the fullerene derivative according to the embodiment of the present invention include C 60 , C 70 , C 76 , C 78 , and higher-order fullerenes, which have high solubility in lubricating oil. from the point, preferably C 60 and C 70, and that the obtained industrially easily a high purity, from the viewpoint coloring of the lubricating oil is small, C 60 is more preferable. Further, in order to reduce the cost of fullerene derivatives, in the synthesis process of the fullerene derivative, it is also possible to use a mix fullerene is a mixture of other fullerene C 60. When mixed fullerenes are used, the mass ratio of C 60 is preferably 50% or more of the total.
本発明のフラーレン誘導体が有するパーフルオロポリエーテル鎖を含む基のパーフルオロポリエーテル鎖の部分は、−(CF2)xO−(式中xは1〜5の整数である)で表される構造を有することが好ましい。さらに、−(CF2CF2O)y(CF2O)z−で表される部分構造を有することがより好ましい。ここで、y及びzは1〜50の整数である。前記パーフルオロポリエーテル鎖を含む基の、パーフルオロポリエーテル鎖以外の部分は特に限定されない。前記パーフルオロポリエーテル鎖を含む基の末端部の構造としては、トリフルオロメチル基やパーフルオロブチル基などのパーフルオロアルキル基、メチル基やブチル基などのアルキル基、フェニル基やナフチル基などのアリール基、またはベンジル基やフェニルプロピル基などのアラルキル基を含む構造が好ましく、その中でもパーフルオロアルキル基がより好ましく、パーフルオロブチル基が特に好ましい。前記構造を有すると、フラーレン誘導体は、パーフルオロポリエーテル油への溶解性が向上する。The portion of the perfluoropolyether chain of the group containing the perfluoropolyether chain contained in the fullerene derivative of the present invention is represented by-(CF 2 ) x O- (x is an integer of 1 to 5 in the formula). It preferably has a structure. Further, it is more preferable to have a partial structure represented by − (CF 2 CF 2 O) y (CF 2 O) z −. Here, y and z are integers of 1 to 50. The portion of the group containing the perfluoropolyether chain other than the perfluoropolyether chain is not particularly limited. The structure of the terminal portion of the group containing the perfluoropolyether chain includes a perfluoroalkyl group such as a trifluoromethyl group and a perfluorobutyl group, an alkyl group such as a methyl group and a butyl group, and a phenyl group and a naphthyl group. A structure containing an aryl group or an aralkyl group such as a benzyl group or a phenylpropyl group is preferable, among which a perfluoroalkyl group is more preferable, and a perfluorobutyl group is particularly preferable. Having the above structure makes the fullerene derivative more soluble in perfluoropolyether oil.
なお、前記パーフルオロポリエーテル鎖を含む基は、直接的にフラーレン骨格に接合してもよく、接合構造を介して、フラーレン骨格に接合してもよい。接合構造について、特に限定されないが、アリール基を含む接合構造が好ましい。また、前記パーフルオロポリエーテル鎖を含む基は、直接的にアリール基と連結することがより好ましい。前記パーフルオロポリエーテル鎖を含む基のアリール基との連結部の構造としては、例えば、エーテル結合やエステル結合を含む構造が挙げられ、その中でもエーテル結合を含む構造が好ましく、特に−OCH2−を含む構造が好ましい。The group containing the perfluoropolyether chain may be directly bonded to the fullerene skeleton, or may be bonded to the fullerene skeleton via a bonding structure. The bonding structure is not particularly limited, but a bonding structure containing an aryl group is preferable. Further, it is more preferable that the group containing the perfluoropolyether chain is directly linked to the aryl group. Examples of the structure of the linking portion of the group containing the perfluoropolyether chain with the aryl group include a structure containing an ether bond and an ester bond, and among them, a structure containing an ether bond is preferable, and particularly −OCH 2 −. A structure containing is preferable.
本発明のフラーレン誘導体は、特に以下の式(1)または式(2)の構造を有するものが最も好ましい。 The fullerene derivative of the present invention is most preferably one having the structure of the following formula (1) or formula (2).
より具体的に、例えば、R1、R2としては、互いに独立に、水素原子、メチル基やエチル基などのアルキル基、フェニル基やナフチル基などのアリール基、ベンジル基やフェニルプロピル基などのアラルキル基が挙げられ、その中でもアルキル基またはアリール基であることが好ましく、メチル基またはフェニル基であることが特に好ましい。A1、A2としては、互いに独立に、−OCH2(CF2O)m(CF2CF2O)nR3で表されるものが挙げられる。ここで、R3としては、炭素数1〜5のアルキル基、パーフルオロアルキル基が挙げられ、その中でもパーフルオロアルキル基であることが好ましく、パーフルオロブチル基であることが特に好ましい。なお、m、nはそれぞれ独立に1〜50の整数を表す。本発明のフラーレン誘導体は上記の構造を有すれば、パーフルオロポリエーテル油への溶解性が高まる。
More specifically, for example, R 1 and R 2 are independent of each other, such as a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group or a naphthyl group, a benzyl group or a phenylpropyl group. Examples thereof include an aralkyl group, of which an alkyl group or an aryl group is preferable, and a methyl group or a phenyl group is particularly preferable. Examples of A 1 and A 2 include those represented by −OCH 2 (CF 2 O) m (CF 2 CF 2 O) n R 3 independently of each other. Here, examples of R 3 include an alkyl group having 1 to 5 carbon atoms and a perfluoroalkyl group, and among them, a perfluoroalkyl group is preferable, and a perfluorobutyl group is particularly preferable. Note that m and n independently represent integers of 1 to 50. If the fullerene derivative of the present invention has the above structure, its solubility in perfluoropolyether oil is enhanced.
なお、上記式(1)または式(2)の構造を有するフラーレン誘導体は、WO2017/006812号公報または特開2017−14192号公報に記載の合成法により、作製することができる。 The fullerene derivative having the structure of the above formula (1) or formula (2) can be produced by the synthetic method described in WO2017 / 006812 or JP2017-14192.
本実施形態の潤滑油組成物のフラーレン誘導体の含有量は、基油100質量部に対して、0.0001〜0.2000質量部であり、好ましくは0.0010〜0.2000質量部であり、より好ましくは0.0010〜0.1000質量部である。フラーレン誘導体の含有量が上記範囲内であれば、フラーレン誘導体は、パーフルオロポリエーテル油に溶解でき、十分な耐摩耗性向上の効果が期待できる。また、フラーレン誘導体の含有量は上記の範囲内であれば、高温、高圧の使用条件下においても、フラーレン誘導体の分解または凝集による固体物の生成が少なく、長時間にわたって、優れた潤滑性能を維持することができる。 The content of the fullerene derivative in the lubricating oil composition of the present embodiment is 0.0001 to 0.2000 parts by mass, preferably 0.0010 to 0.2000 parts by mass, based on 100 parts by mass of the base oil. , More preferably 0.0010 to 0.1000 parts by mass. When the content of the fullerene derivative is within the above range, the fullerene derivative can be dissolved in perfluoropolyether oil, and a sufficient effect of improving wear resistance can be expected. Further, if the content of the fullerene derivative is within the above range, even under high temperature and high pressure usage conditions, the formation of solid matter due to decomposition or aggregation of the fullerene derivative is small, and excellent lubrication performance is maintained for a long period of time. can do.
なお、フラーレン誘導体の含有量は上記範囲内であれば、潤滑油組成物のラメラ長を延長する効果も十分期待できる。ラメラ長が延長することで、潤滑油組成物の成膜性が向上され、少量の潤滑油組成物で油膜が出来、さらに潤滑油組成物の漏洩防止効果も得られる。また、ラメラ長が長いほど、油膜が切れにくくなり、耐焼付性が高まる。 If the content of the fullerene derivative is within the above range, the effect of extending the lamella length of the lubricating oil composition can be sufficiently expected. By extending the lamella length, the film-forming property of the lubricating oil composition is improved, an oil film can be formed with a small amount of the lubricating oil composition, and a leakage prevention effect of the lubricating oil composition can be obtained. Further, the longer the lamella length, the more difficult it is for the oil film to break, and the higher the seizure resistance.
本実施形態に係る潤滑油組成物は、フラーレン誘導体の分解又は凝集による生成した固体粒子がなく、又は極めて少ないことが好ましい。即ち、潤滑油組成物10mlあたり長径1μm以上の固体粒子が1個未満であることが好ましく、0.1個未満であることはより好ましい。確認は、後述する実施例の方法により行うことができる。
(添加剤)
本実施形態の潤滑油組成物に、諸特性を改善するために、フラーレン誘導体以外の添加剤を更なる配合することができる。このような添加剤としては、特に限定されないが、例えば、市販の酸化防止剤、粘度指数向上剤、清浄分散剤、腐食防止剤、油性向上剤、錆止め添加剤、消泡剤、加水分解抑制剤などを配合することができる。The lubricating oil composition according to the present embodiment preferably has no or very few solid particles produced by decomposition or aggregation of the fullerene derivative. That is, it is preferable that the number of solid particles having a major axis of 1 μm or more per 10 ml of the lubricating oil composition is less than 1, and more preferably less than 0.1. The confirmation can be performed by the method of the embodiment described later.
(Additive)
Additives other than fullerene derivatives can be further added to the lubricating oil composition of the present embodiment in order to improve various properties. Such additives are not particularly limited, but are, for example, commercially available antioxidants, viscosity index improvers, detergent dispersants, corrosion inhibitors, oiliness improvers, rust preventive additives, defoamers, and hydrolysis inhibitors. Etc. can be blended.
本発明の潤滑油組成物は、パーフルオロポリエーテル油からなる基油、フラーレン誘導体、及び場合によりその他の成分を、通常の混合方法を用いて混合することで得られることができる。混合方法としては、特に限定されなく、スターラー、超音波分散装置、ホモジナイザー、ボールミル、ビーズミルなどを用いることが可能である。また、場合により、混合することで得た潤滑油組成物中に、フラーレン誘導体の析出物、原料由来の不溶物および混合過程中で混入した不溶物等の固体物が存在する可能性がある。これらの固体物の存在により、摩擦係数が上昇する虞があるため、混合工程後、固体物を除去するための工程を設けでもよい。除去方法として、濾過による除去方法、遠心分離による除去方法、それら除去方法の組み合わせなどを挙げることができる。
(用途)
本実施形態の潤滑油組成物は、耐ガス性,低揮発性、高温特性、不燃性であることが特徴で、半導体真空ポンプ、高温ロール軸受、酸素ブロアー、電着塗装オーブン、フィルム延伸機 、ユルゲーター、複写機、レーザープリンター(LBP)、コーン製造機、クリーンルーム、真空機器、遠心分離機各種バルブ、航空機器、宇宙機器などの各種用途に使用することができる。The lubricating oil composition of the present invention can be obtained by mixing a base oil consisting of a perfluoropolyether oil, a fullerene derivative, and optionally other components by using a usual mixing method. The mixing method is not particularly limited, and a stirrer, an ultrasonic disperser, a homogenizer, a ball mill, a bead mill, or the like can be used. In some cases, the lubricating oil composition obtained by mixing may contain solid substances such as a precipitate of a fullerene derivative, an insoluble matter derived from a raw material, and an insoluble matter mixed in during the mixing process. Since the coefficient of friction may increase due to the presence of these solids, a step for removing the solids may be provided after the mixing step. Examples of the removal method include a removal method by filtration, a removal method by centrifugation, and a combination of these removal methods.
(Use)
The lubricating oil composition of the present embodiment is characterized by gas resistance, low volatility, high temperature characteristics, and nonflammability, and is characterized by a semiconductor vacuum pump, a high temperature roll bearing, an oxygen blower, an electrodeposition coating oven, a film stretching machine, and the like. It can be used in various applications such as lubricants, copiers, laser printers (LBPs), cone making machines, clean rooms, vacuum equipment, various centrifuge valves, aviation equipment, and space equipment.
以上、本発明の好ましい実施形態について述べたが、本発明は特定の実施の形態に限定されるものではなく、特許請求の範囲内に記載された本発明の要旨の範囲内において、種々の変形・変更が可能である。 Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the specific embodiments, and various modifications are made within the scope of the gist of the present invention described in the claims.・ Can be changed.
以下、本発明の実施例について説明する。なお、本発明は以下の実施例のみに限定されるものではない。
(NMR分析)
1H−NMRは下記の条件にて測定した。
装置:日本電子製 JNM−EX270
試料調製:試料(約10mg〜30mg)をCDCl3/ヘキサフルオロベンゼン混合溶媒(約0.5mL)に溶解させた後、直径5mmのNMR試料管に入れた。
測定温度:室温
基準物質:溶媒に添加されたテトラメチルシランのシグナルを基準とした。
(耐摩耗性の評価)
ボールオンディスクトライボメーター(Antonparr製)試験により、潤滑油組成物の耐摩耗性を評価した。ボールとして、径6mm(SUJ2)、ディスクとして、径13mm、厚さ5mm(SUJ2)をそれぞれ用い、荷重25N、回転速度10rpm、回転数1000回の条件で摩耗痕径(mm)を測定して評価した。本評価においては、摩耗痕径が小さいほど、摩耗特性に優れることを意味する
(ラメラ長の測定)
潤滑油組成物のラメラ長は、du Nouy法(JIS K2241)により,自動表面張力測定装置DY−300(協和界面科学株式会社製)を用いて、測定した。潤滑油組成物20gを専用のシャーレに入れ、下記の測定条件で、引き上げ張力(表面張力)のピークから液膜が切れるまでの長さ(ラメラ長)を測定した。
<測定条件>
白金リング直径:14.40mm
線材直径:0.4mm
白金リング引下げ速度:12mm/min
接液感度:3mN/m
ステージ下降速度:0.2mm/s
ステージ上昇速度:0.2mm/s
プリウェット下降速度:0.7mm/s
プリウェット上昇速度:0.7mm/s
プリウェット浸漬距離:2.5mm
プリウェット時間:1s
検体調整用容器(シャーレ):50mlガラス瓶
繰り返し測定数:n=10回の平均値を1セットとし、2セットの平均値を採用した。
(長径1μm以上の固体粒子数の測定)
潤滑油組成物を30℃で3日間放置後、潤滑油組成物10mlを0.1μmのメンブランフィルターで濾過し、この濾過面を走査型電子顕微鏡で観察し、長径1μm以上の固体粒子を数えた。この濾過〜走査型電子顕微鏡観察までを10回繰り返し、固体粒子数の平均値を得た。
(フラーレン誘導体Aの合成)
フッ素化トリエチレングリコールモノブチルエーテル(化学式:CF3CF2CF2CF2(OCF2CF2)2OCF2CH2OH、Exfluor社製、13g、24mmol)、ピリジン(2.3g、29mmol)をジクロロメタン(120mL)に加え、得られた溶液にトリフルオロメタンスルホン酸無水物(8.2g、29mmol)のジクロロメタン(120mL)溶液を滴下した。室温で16時間攪拌した後、反応混合物を純水(100mL)と飽和炭酸ナトリウム水溶液(100mL)で一度ずつ洗浄した。得られた有機層を濾過した後、ロータリーエバポレーターで濃縮することで、下記の式(3)の構造を有する化合物1(15g、22mmol、収率92%)を淡黄色油状物質として得た。Hereinafter, examples of the present invention will be described. The present invention is not limited to the following examples.
(NMR analysis)
1 1 H-NMR was measured under the following conditions.
Equipment: JEM-EX270 manufactured by JEOL Ltd.
Sample preparation: A sample (about 10 mg to 30 mg) was dissolved in a mixed solvent of CDCl 3 / hexafluorobenzene (about 0.5 mL) and then placed in an NMR sample tube having a diameter of 5 mm.
Measurement temperature: Room temperature Reference substance: The signal of tetramethylsilane added to the solvent was used as a reference.
(Evaluation of wear resistance)
The wear resistance of the lubricating oil composition was evaluated by a ball-on-disc tribometer (manufactured by Antonioparr) test. Using a ball with a diameter of 6 mm (SUJ2) and a disc with a diameter of 13 mm and a thickness of 5 mm (SUJ2), the wear mark diameter (mm) is measured and evaluated under the conditions of a load of 25 N, a rotation speed of 10 rpm, and a rotation speed of 1000 times. did. In this evaluation, the smaller the wear mark diameter, the better the wear characteristics (measurement of lamella length).
The lamella length of the lubricating oil composition was measured by the du Noüy method (JIS K2241) using an automatic surface tension measuring device DY-300 (manufactured by Kyowa Interface Science Co., Ltd.). 20 g of the lubricating oil composition was placed in a special petri dish, and the length from the peak of the pulling tension (surface tension) to the break of the liquid film (lamella length) was measured under the following measurement conditions.
<Measurement conditions>
Platinum ring diameter: 14.40 mm
Wire diameter: 0.4 mm
Platinum ring pulling speed: 12 mm / min
Liquid contact sensitivity: 3 mN / m
Stage descent speed: 0.2 mm / s
Stage climbing speed: 0.2 mm / s
Pre-wet descent speed: 0.7 mm / s
Pre-wet rising speed: 0.7 mm / s
Pre-wet immersion distance: 2.5 mm
Pre-wet time: 1s
Specimen preparation container (Petri dish): 50 ml glass bottle Number of repeated measurements: n = The average value of 10 times was set as one set, and the average value of two sets was adopted.
(Measurement of the number of solid particles with a major axis of 1 μm or more)
After leaving the lubricating oil composition at 30 ° C. for 3 days, 10 ml of the lubricating oil composition was filtered through a 0.1 μm membrane filter, and the filtered surface was observed with a scanning electron microscope to count solid particles having a major axis of 1 μm or more. .. This filtration to scanning electron microscope observation was repeated 10 times, and the average value of the number of solid particles was obtained.
(Synthesis of fullerene derivative A)
Fluorinated triethylene glycol monobutyl ether (chemical formula: CF 3 CF 2 CF 2 CF 2 (OCF 2 CF 2 ) 2 OCF 2 CH 2 OH, Exfluor, 13 g, 24 mmol), pyridine (2.3 g, 29 mmol) in dichloromethane In addition to (120 mL), a solution of trifluoromethanesulfonic anhydride (8.2 g, 29 mmol) in dichloromethane (120 mL) was added dropwise to the obtained solution. After stirring at room temperature for 16 hours, the reaction mixture was washed once with pure water (100 mL) and saturated aqueous sodium carbonate solution (100 mL). The obtained organic layer was filtered and then concentrated on a rotary evaporator to obtain Compound 1 (15 g, 22 mmol, yield 92%) having the structure of the following formula (3) as a pale yellow oily substance.
次に、入口および出口をもつ肉厚のステンレス容器(内径20mm×深さ200mm)に、粗生成物を入れ、容器内の温度を60℃に保ちながら、超臨界二酸化炭素送液ポンプ(日本分光製、PU2086−CO2)を用いて、超臨界二酸化炭素を液化二酸化炭素換算流量5mL/分を容器に送った。容器内の圧力を15〜20MPaの範囲で変化させ、黒色油状のフラーレン誘導体Aを3.0g抽出した。下記の式に示したNMRの分析結果より、フラーレン誘導体Aは以下式(5)の構造を有することが確認された。 Next, put the crude product in a thick stainless steel container (inner diameter 20 mm x depth 200 mm) with an inlet and an outlet, and keep the temperature inside the container at 60 ° C while supercritical carbon dioxide liquid feed pump (JASCO Corporation). , PU2086-CO2) was used to pump supercritical carbon dioxide to a container at a liquefied carbon dioxide equivalent flow rate of 5 mL / min. The pressure in the container was changed in the range of 15 to 20 MPa, and 3.0 g of the black oily fullerene derivative A was extracted. From the NMR analysis results shown in the following formula, it was confirmed that the fullerene derivative A has the structure of the following formula (5).
1H−NMR δ(ppm):2.79(brs、6H)、4.39(br、18H)、6.22(brs、4H)。 1 1 H-NMR δ (ppm): 2.79 (brs, 6H), 4.39 (br, 18H), 6.22 (brs, 4H).
フラーレン誘導体Aの合成と同様に化合物1を作製した。得た化合物1(8.2g、12mmol)と、2',4',6'−トリヒドロキシアセトフェノン一水和物(0.57g、3.0mmol)とをN,N−ジメチルホルムアミド(80mL)に加え、得られた溶液に炭酸セシウム(5.9g、18mmol)を加えた。70℃で2時間攪拌した後、反応混合物を室温まで冷やし、ロータリーエバポレーターで濃縮した。得られた混合物を純水(30mL)とAK―225(30mL)を用いて分液し、さらに水層をAK―225(20mL)で二度抽出した。得られた有機層を水洗し、硫酸マグネシウムにより乾燥した。濾過した後、ロータリーエバポレーターで濃縮することで、赤褐色油状の粗生成物(4.7g)を得た。シリカゲルカラムクロマトグラフィー(展開溶媒:ヘキサン―酢酸エチル(9:1))で精製することで、下記の式(6)の構造を有する化合物3を黄褐色油状物質(3.7g、2.1mmol、収率69%)として得た。
Compound 1 was prepared in the same manner as in the synthesis of the fullerene derivative A. The obtained compound 1 (8.2 g, 12 mmol) and 2', 4', 6'-trihydroxyacetophenone monohydrate (0.57 g, 3.0 mmol) were added to N, N-dimethylformamide (80 mL). In addition, cesium carbonate (5.9 g, 18 mmol) was added to the obtained solution. After stirring at 70 ° C. for 2 hours, the reaction mixture was cooled to room temperature and concentrated on a rotary evaporator. The obtained mixture was separated using pure water (30 mL) and AK-225 (30 mL), and the aqueous layer was further extracted twice with AK-225 (20 mL). The obtained organic layer was washed with water and dried over magnesium sulfate. After filtration, the mixture was concentrated on a rotary evaporator to obtain a crude product (4.7 g) of reddish brown oil. By purifying with silica gel column chromatography (developing solvent: hexane-ethyl acetate (9: 1)), compound 3 having the structure of the following formula (6) was obtained as a yellowish brown oily substance (3.7 g, 2.1 mmol, The yield was 69%).
次に、入口および出口をもつ肉厚のステンレス容器(内径20mm×深さ200mm)に、粗生成物を入れ、容器内の温度を60℃に保ちながら、超臨界二酸化炭素送液ポンプ(日本分光製、PU2086−CO2)を用いて、超臨界二酸化炭素を液化二酸化炭素換算流量5mL/分を容器に送った。容器内の圧力を12〜18MPaの範囲で変化させ、黒色油状のフラーレン誘導体Bを1.0g抽出した。下記に示したNMRの分析結果より、フラーレン誘導体Bは下記式(8)の構造を有することが確認された。 Next, put the crude product in a thick stainless steel container (inner diameter 20 mm x depth 200 mm) with an inlet and an outlet, and keep the temperature inside the container at 60 ° C while supercritical carbon dioxide liquid feed pump (JASCO Corporation). , PU2086-CO2) was used to pump supercritical carbon dioxide to a container at a liquefied carbon dioxide equivalent flow rate of 5 mL / min. The pressure in the container was changed in the range of 12 to 18 MPa, and 1.0 g of the black oily fullerene derivative B was extracted. From the NMR analysis results shown below, it was confirmed that the fullerene derivative B has the structure of the following formula (8).
1H−NMR δ(ppm):2.63(s、3H)、4.46(t、4H)、4.63(t、2H)、6.32(s、2H)。 1 1 H-NMR δ (ppm): 2.63 (s, 3H), 4.46 (t, 4H), 4.63 (t, 2H), 6.32 (s, 2H).
パーフルオロポリエーテル油として、ダイキン工業(株)製 DEMNUM S−20(F(CF2CF2CF2O)jCF2CF3、平均分子量2700)、およびNOK(株)製:BRAAIERTA J−25(C3F7O〔CF(CF3)CF2O〕kC2F5、kは2〜100の整数である)を用いる。
(実施例1)
基油としてBRAAIERTA J−25 100gに、フラーレン誘導体Aを0.001g添加し、室温でスターラーを用いて36時間撹拌して溶解し、潤滑油組成物を得た。得た潤滑油組成物のフラーレン誘導体の含有量は、基油100質量部に対して、0.0010質量部である。前記の測定方法で、潤滑油組成物の耐摩耗性評価、及びラメラ長と長径1μm以上の固体粒子数の測定を実施し、結果を表1に纏めた。なお、潤滑油組成物において、フラーレン誘導体の含有量は、基油100質量部に対して、フラーレン誘導体の仕込み量より算出した。
(実施例2〜9、比較例1〜4)
基油と、フラーレン誘導体と、その含有量を除き、実施例1と同様に潤滑油組成物を調製し、各測定を実施した。なお、基油と、フラーレン誘導体と、その含有量は、表1に記載の組成を有する潤滑油組成物となるようにそれぞれ調整した。
As perfluoropolyether oil, DEFMNUM S-20 (F (CF 2 CF 2 CF 2 O) j CF 2 CF 3 , average molecular weight 2700) manufactured by Daikin Industries, Ltd., and BRAAIERTA J-25 manufactured by NOK Co., Ltd. (C 3 F 7 O [CF (CF 3 ) CF 2 O] k C 2 F 5 , k is an integer of 2 to 100) is used.
(Example 1)
0.001 g of fullerene derivative A was added to 100 g of BRAAIERTA J-25 as a base oil, and the mixture was dissolved by stirring at room temperature for 36 hours using a stirrer to obtain a lubricating oil composition. The content of the fullerene derivative in the obtained lubricating oil composition is 0.0010 parts by mass with respect to 100 parts by mass of the base oil. Using the above-mentioned measuring method, the abrasion resistance of the lubricating oil composition was evaluated, and the lamella length and the number of solid particles having a major axis of 1 μm or more were measured, and the results are summarized in Table 1. In the lubricating oil composition, the content of the fullerene derivative was calculated from the amount of the fullerene derivative charged with respect to 100 parts by mass of the base oil.
(Examples 2 to 9, Comparative Examples 1 to 4)
A lubricating oil composition was prepared in the same manner as in Example 1 except for the base oil, the fullerene derivative, and their contents, and each measurement was carried out. The base oil, the fullerene derivative, and their contents were adjusted so as to be a lubricating oil composition having the composition shown in Table 1, respectively.
本出願は2018年12月21日に出願した日本国特許出願第2018−240098号に基づくものであり、その全内容は参照することによりここに組み込まれる。 This application is based on Japanese Patent Application No. 2018-24008 filed on December 21, 2018, the entire contents of which are incorporated herein by reference.
Claims (5)
パーフルオロポリエーテル鎖を含む基を有するフラーレン誘導体とを有し、
前記基油100質量部に対して、前記フラーレン誘導体を0.0001〜0.2000質量部を含有する潤滑油組成物。Perfluoropolyether oil as a base oil and
With a fullerene derivative having a group containing a perfluoropolyether chain,
A lubricating oil composition containing 0.0001 to 0.2000 parts by mass of the fullerene derivative with respect to 100 parts by mass of the base oil.
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