JP2023071022A - Oil agent additive and oil agent composition - Google Patents
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- 239000000654 additive Substances 0.000 title claims abstract description 57
- 230000000996 additive effect Effects 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 title abstract description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 69
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 33
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 100
- 239000010687 lubricating oil Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000010705 motor oil Substances 0.000 claims description 3
- 239000012208 gear oil Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 24
- 150000002118 epoxides Chemical class 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 8
- -1 Ether alcohols Chemical class 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 150000001414 amino alcohols Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003879 lubricant additive Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- 101100403761 Arabidopsis thaliana MTM2 gene Proteins 0.000 description 1
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
Description
本発明は、油剤添加剤、及び前記油剤添加剤と油剤を含有する油剤組成物に関する。 TECHNICAL FIELD The present invention relates to an oil agent additive and an oil agent composition containing the oil agent additive and the oil agent.
エポキシアルカンと多価アルコールとの反応によって得られるエーテルアルコールは、乳化剤及び界面活性剤などの原料として有用である。 Ether alcohols obtained by reacting epoxyalkanes and polyhydric alcohols are useful as raw materials for emulsifiers, surfactants, and the like.
例えば、特許文献１では、炭素数８～２０のエポキシアルカンと炭素原子１～１０個及びアルコール性水酸基１～４個を有するモノ又はポリ官能性アルコールとの反応によって得られるエーテルアルコールが開示されている。 For example, Patent Document 1 discloses an ether alcohol obtained by reacting an epoxyalkane having 8 to 20 carbon atoms with a mono- or polyfunctional alcohol having 1 to 10 carbon atoms and 1 to 4 alcoholic hydroxyl groups. there is
一方、特許文献２には、炭素数８～２２の炭化水素基を有するモノグリセリド（グリセリンの３つのヒドロキシル基のうち１つに脂肪酸がエステル結合したグリセリン脂肪酸エステル）を含有する内燃機関用潤滑油組成物が開示されている。 On the other hand, in Patent Document 2, a lubricating oil composition for an internal combustion engine containing a monoglyceride having a hydrocarbon group with 8 to 22 carbon atoms (glycerin fatty acid ester in which a fatty acid is ester-bonded to one of the three hydroxyl groups of glycerin) things are disclosed.
当該モノグリセリドは、摩擦調整剤として潤滑油組成物に添加されている。 Such monoglycerides have been added to lubricating oil compositions as friction modifiers.
しかしながら、特許文献２に記載のモノグリセリドは、潤滑油に溶けにくく、摩擦係数を低下させるために添加量を多くすると潤滑油組成物中に析出するという問題があった。 However, the monoglyceride described in Patent Document 2 has a problem that it is difficult to dissolve in lubricating oil and precipitates in the lubricating oil composition when added in a large amount to lower the coefficient of friction.
本発明は、上記のような状況を鑑みてなされたものであり、油剤に溶けやすく、摩擦係数を低下させる効果に優れる油剤添加剤、及び前記油剤添加剤を含有する油剤組成物を提供する。 The present invention has been made in view of the above circumstances, and provides an oil agent additive that is easily soluble in an oil agent and has an excellent effect of lowering the coefficient of friction, and an oil agent composition containing the oil agent additive.
本発明者は鋭意検討を重ねた結果、特定構造の化合物により、上記課題を解決しうることを見出した。 As a result of extensive studies, the inventors have found that the above problems can be solved by a compound having a specific structure.
すなわち、本発明は、下記化学式（１）で表される化合物を少なくとも１種含有する油剤添加剤、に関する。
従来の潤滑油添加剤として用いられてきたモノグリセリドは、モノグリセリドの水酸基が金属に吸着し、モノグリセリドの直鎖アルキル基が潤滑油側に向くことで油膜を形成して摩擦を低減する。より強固な油膜を形成して摩擦係数の低減効果を向上するためにはモノグリセリドの直鎖アルキル基を長くする必要がある。しかし、モノグリセリドの直鎖アルキル基が長いほど、モノグリセリドの融点がより高くなるため潤滑油に対する溶解性が低下すると考えられる。 Monoglyceride, which has been used as a conventional lubricating oil additive, reduces friction by forming an oil film when the hydroxyl group of monoglyceride adsorbs to metal and the linear alkyl group of monoglyceride faces the lubricating oil side. In order to form a stronger oil film and improve the effect of reducing the coefficient of friction, it is necessary to lengthen the linear alkyl group of the monoglyceride. However, it is believed that the longer the linear alkyl group of the monoglyceride, the higher the melting point of the monoglyceride and thus the lower the solubility in lubricating oils.
一方、本発明の化学式（１）で表される化合物は、炭素鎖の内部に特定の第三級アミノ基と水酸基を有する特徴ある構造を有しているため、融点が低く、油剤に対する溶解性に優れており、しかも摩擦係数を低下させる効果に優れていると考えられる。 On the other hand, the compound represented by the chemical formula (1) of the present invention has a characteristic structure having a specific tertiary amino group and a hydroxyl group inside the carbon chain, so it has a low melting point and is soluble in oils. It is considered to be excellent in the effect of lowering the friction coefficient.
以下、本発明について詳細に説明する。 The present invention will be described in detail below.
＜油剤添加剤＞
本発明の油剤添加剤は、下記化学式（１）で表される化合物（以下、アミノアルコールともいう）を少なくとも１種含有する。また、本発明の油剤添加剤は、下記化学式（１）で表される化合物からなるものであってよい。また、本発明の油剤添加剤は、下記化学式（１）で表される化合物の１種以上からなるものであってよい。
The oil additive of the present invention contains at least one compound represented by the following chemical formula (1) (hereinafter also referred to as aminoalcohol). Further, the oil agent additive of the present invention may consist of a compound represented by the following chemical formula (1). Further, the oil agent additive of the present invention may consist of one or more compounds represented by the following chemical formula (1).
Ｒ１及びＲ２はそれぞれ炭素数１以上３３以下の脂肪族炭化水素基であり、摩擦係数を低下させる観点から、好ましくは直鎖又は分岐アルキル基（分岐鎖アルキル基ともいう）であり、より好ましくは直鎖アルキル基である。前記脂肪族炭化水素基は、本発明の効果を妨げない限り、ヒドロキシ基、ケトン基、カルボキシル基、アリール基、及びアルコキシ基等の置換基を有していてもよい。Ｒ１及びＲ２は、同じ脂肪族炭化水素基であってもよく、異なる脂肪族炭化水素基であってもよい。また、Ｒ１及びＲ２の置換基の数は、それぞれ、油剤に対する溶解性の観点から、Ｒ１及びＲ２において合計で、好ましくは５以下、より好ましくは３以下、更に好ましくは１以下、より更に好ましくは０（すなわち置換基を有さない）である。 Each of R 1 and R 2 is an aliphatic hydrocarbon group having 1 to 33 carbon atoms, and from the viewpoint of reducing the coefficient of friction, preferably a linear or branched alkyl group (also referred to as a branched alkyl group). A straight-chain alkyl group is preferred. The aliphatic hydrocarbon group may have a substituent such as a hydroxy group, a ketone group, a carboxyl group, an aryl group, and an alkoxy group as long as the effects of the present invention are not impaired. R 1 and R 2 may be the same aliphatic hydrocarbon group or different aliphatic hydrocarbon groups. From the viewpoint of solubility in oil agents, the total number of substituents on R 1 and R 2 is preferably 5 or less, more preferably 3 or less, and still more preferably 1 or less. Even more preferably, it is 0 (ie, has no substituents).
Ｒ１及びＲ２の合計炭素数は２以上３４以下であり、摩擦係数を低下させる観点から、好ましくは１２以上、より好ましくは１４以上、更に好ましくは１６以上であり、油剤に対する溶解性の観点から、好ましくは２２以下、より好ましくは２０以下、更に好ましくは１８以下、より更に好ましくは１６以下である。なお、Ｒ１及びＲ２の脂肪族炭化水素基が炭素を含む置換基を有する場合、その置換基の炭素数は、Ｒ１及びＲ２の合計炭素数に含まれる。 The total carbon number of R 1 and R 2 is 2 or more and 34 or less, preferably 12 or more, more preferably 14 or more, and still more preferably 16 or more from the viewpoint of reducing the coefficient of friction, and from the viewpoint of solubility in oil agents. Therefore, it is preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, and even more preferably 16 or less. When the aliphatic hydrocarbon groups of R 1 and R 2 have a substituent containing carbon, the carbon number of the substituent is included in the total carbon number of R 1 and R 2 .
Ａは－Ｎ（Ｒ３）（Ｒ４）であり、Ｒ３はメチル基又は炭素数２以上４以下のヒドロキシアルキル基、Ｒ４は炭素数２以上４以下のヒドロキシアルキル基である。Ｒ３は、油剤に対する溶解性の観点から、好ましくは炭素数２以上４以下のヒドロキシアルキル基である。Ｒ３及びＲ４のそれぞれのヒドロキシアルキル基の炭素数は、油剤に対する溶解性の観点から、好ましくは２以上３以下、より好ましくは２である。 A is -N(R 3 )(R 4 ), R 3 is a methyl group or a hydroxyalkyl group having 2 to 4 carbon atoms, and R 4 is a hydroxyalkyl group having 2 to 4 carbon atoms. R 3 is preferably a hydroxyalkyl group having 2 or more and 4 or less carbon atoms from the viewpoint of solubility in oil agents. The number of carbon atoms in the hydroxyalkyl groups of R 3 and R 4 is preferably 2 or more and 3 or less, more preferably 2, from the viewpoint of solubility in oil agents.
Ｘは単結合又は炭素数１以上５以下の脂肪族炭化水素基であり、油剤に対する溶解性の観点から、好ましくは単結合又は炭素数１以上３以下の脂肪族炭化水素基、より好ましくは単結合又は炭素数１以上２以下の脂肪族炭化水素基、更に好ましくは単結合又は炭素数１の脂肪族炭化水素基、より更に好ましくは単結合である。 X is a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, preferably a single bond or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a single It is a bond or an aliphatic hydrocarbon group having 1 to 2 carbon atoms, more preferably a single bond or an aliphatic hydrocarbon group having 1 carbon atom, still more preferably a single bond.
Ｒ１とＲ２とＸの合計炭素数は２以上３９以下であり、摩擦係数を低下させる観点から、好ましくは１２以上、より好ましくは１４以上、更に好ましくは１６以上であり、油剤に対する溶解性の観点から、好ましくは２４以下、より好ましくは２２以下、更に好ましくは２０以下、より更に好ましくは１８以下、より更に好ましくは１６以下である。 The total number of carbon atoms of R 1 , R 2 and X is 2 or more and 39 or less, preferably 12 or more, more preferably 14 or more, and still more preferably 16 or more from the viewpoint of reducing the coefficient of friction. from the viewpoint of, it is preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, even more preferably 18 or less, and even more preferably 16 or less.
Ｘが前記脂肪族炭化水素基である場合、油剤に対する溶解性の観点から、好ましくは直鎖又は分岐アルキル基であり、より好ましくは直鎖アルキル基である。また、Ｘの脂肪族炭化水素基としては、他に、アルキレン基（アルカンジイル基）のような二価の炭化水素基が挙げられる。 When X is the aliphatic hydrocarbon group, it is preferably a linear or branched alkyl group, more preferably a linear alkyl group, from the viewpoint of solubility in oil agents. Further, the aliphatic hydrocarbon group for X also includes a divalent hydrocarbon group such as an alkylene group (alkanediyl group).
前記油剤添加剤は、油剤に対する溶解性の観点から、Ｒ１とＲ２の合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含むことが好ましい。 From the viewpoint of solubility in oil, the oil additive may contain two or more compounds in which the total number of carbon atoms of R 1 and R 2 is the same and the number of carbon atoms of each of R 1 and R 2 is different. preferable.
前記油剤添加剤は、油剤に対する溶解性の観点から、Ｒ１とＲ２とＸの合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含むことが好ましい。 The oil additive contains two or more compounds in which R 1 , R 2 and X have the same total carbon number and R 1 and R 2 have different carbon numbers from the viewpoint of solubility in the oil. is preferred.
前記油剤添加剤は、油剤に対する溶解性の観点から、Ｘが単結合又は炭素数１以上３以下の脂肪族炭化水素基であり、Ｒ１とＲ２の合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含むことが好ましい。 In the oil additive, from the viewpoint of solubility in the oil, X is a single bond or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, R 1 and R 2 have the same total carbon number, and R It is preferable to include two or more compounds in which each of 1 and R 2 has a different number of carbon atoms.
前記油剤添加剤は、油剤に対する溶解性の観点から、Ｘが単結合又は炭素数１以上３以下の脂肪族炭化水素基であり、Ｒ１とＲ２とＸの合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含むことが好ましい。 In the oil additive, from the viewpoint of solubility in the oil, X is a single bond or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and the total number of carbon atoms of R 1 , R 2 and X is the same, Moreover, it preferably contains two or more kinds of compounds in which each of R 1 and R 2 has a different number of carbon atoms.
前記油剤添加剤は、油剤に対する溶解性の観点から、Ｘが単結合又は炭素数１以上２以下の脂肪族炭化水素基であり、Ｒ１とＲ２の合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含むことがより好ましい。 In the oil additive, from the viewpoint of solubility in the oil, X is a single bond or an aliphatic hydrocarbon group having 1 to 2 carbon atoms, R 1 and R 2 have the same total carbon number, and R It is more preferable to contain two or more compounds in which the number of carbon atoms in each of 1 and R 2 is different.
前記油剤添加剤は、油剤に対する溶解性の観点から、Ｘが単結合又は炭素数１以上２以下の脂肪族炭化水素基であり、Ｒ１とＲ２とＸの合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含むことがより好ましい。 In the oil additive, from the viewpoint of solubility in the oil, X is a single bond or an aliphatic hydrocarbon group having 1 or more and 2 or less carbon atoms, and the total number of carbon atoms of R 1 , R 2 and X is the same, Moreover, it is more preferable to include two or more compounds in which the number of carbon atoms in each of R 1 and R 2 is different.
前記油剤添加剤は、油剤に対する溶解性の観点から、Ｘが単結合又は炭素数１の脂肪族炭化水素基であり、Ｒ１とＲ２の合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含むことが更に好ましい。 From the viewpoint of solubility in the oil agent, the oil additive is such that X is a single bond or an aliphatic hydrocarbon group having 1 carbon atom, R 1 and R 2 have the same total number of carbon atoms, and R 1 and R It is further preferable to include two or more compounds each having a different number of carbon atoms in 2 .
前記油剤添加剤は、油剤に対する溶解性の観点から、Ｘが単結合又は炭素数１の脂肪族炭化水素基であり、Ｒ１とＲ２とＸの合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含むことが更に好ましい。 From the viewpoint of solubility in the oil agent, the oil additive is such that X is a single bond or an aliphatic hydrocarbon group having 1 carbon atom, R 1 , R 2 and X have the same total number of carbon atoms, and R 1 and R 2 each having a different number of carbon atoms are more preferably included.
前記油剤添加剤は、油剤に対する溶解性の観点から、Ｘが単結合であり、Ｒ１とＲ２の合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含むことがより更に好ましい。 From the viewpoint of solubility in the oil agent, the oil additive has two types in which X is a single bond, the total number of carbon atoms in R 1 and R 2 is the same, and the number of carbon atoms in each of R 1 and R 2 is different. It is even more preferable to contain the above compounds.
前記油剤添加剤が、Ｘが単結合であり、Ｒ１とＲ２の合計炭素数が異なる２種以上の化合物を含有する場合、油剤に対する溶解性の観点から、Ｒ１とＲ２の合計炭素数が、１４である化合物、及び１６である化合物の合計含有量は、好ましくは７５質量％以上、より好ましくは８５質量％以上、更に好ましくは９５質量％以上、より更に好ましくは１００質量％である。 When the oil additive contains two or more compounds in which X is a single bond and the total carbon number of R 1 and R 2 is different, from the viewpoint of solubility in the oil agent, the total carbon of R 1 and R 2 The total content of the compound whose number is 14 and the compound whose number is 16 is preferably 75% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, and still more preferably 100% by mass. be.
前記油剤添加剤が、化学式（１）で表される化合物において、Ｒ１とＲ２の合計炭素数が同じであり、かつＲ１とＲ２のそれぞれの炭素数が異なる２種以上の化合物を含有する場合、油剤に対する溶解性の観点から、Ｒ１の炭素数が５以上かつＲ２の炭素数が５以上の化合物の含有割合は、好ましくは１０質量％以上、より好ましくは２０質量％以上、更に好ましくは３０質量％以上であり、好ましくは９０質量％以下、より好ましくは８０質量％以下、更に好ましくは７０質量％以下である。Ｒ１の炭素数が５以上かつＲ２の炭素数が５以上の化合物の含有割合は、例えば、アミノアルコールを、内部オレフィンを原料として製造する場合、原料の内部オレフィンの二重結合分布から推定することができる。 The oil additive is a compound represented by the chemical formula (1), wherein two or more compounds having the same total carbon number of R 1 and R 2 and different carbon numbers of R 1 and R 2 are used. When it is contained, the content of the compound in which R 1 has 5 or more carbon atoms and R 2 has 5 or more carbon atoms is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of solubility in oil agents. , more preferably 30% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. The content ratio of the compound in which R 1 has 5 or more carbon atoms and R 2 has 5 or more carbon atoms is estimated from the double bond distribution of the internal olefin of the raw material, for example, when an amino alcohol is produced using an internal olefin as a raw material. can do.
前記アミノアルコールの融点は、油剤に対する溶解性の観点から、好ましくは３０℃以下、より好ましくは２０℃以下、更に好ましくは１０℃以下であり、また、－２００℃以上であってよい。 The melting point of the amino alcohol is preferably 30° C. or lower, more preferably 20° C. or lower, still more preferably 10° C. or lower, and may be −200° C. or higher, from the viewpoint of solubility in oil agents.
前記アミノアルコールの製造方法は特に制限されず、例えば、内部オレフィンの二重結合を過酸化水素、過ギ酸、過酢酸等の過酸化物により酸化して内部エポキシドを合成し、得られた内部エポキシドに２級のアルカノールアミンを反応させることにより製造することができる。２級のアルカノールアミンとしては、ヒドロキシアルキル基が炭素数２以上４以下のアルカノールアミンを用いることができる。前記アルカノールアミンとしては、例えば、Ｎ－メチルエタノールアミン、ジエタノールアミン、ジプロパノールアミン、及びジイソプロパノールアミン等が挙げられる。なお、前記製造方法により得られる前記アミノアルコールは、Ｒ１又はＲ２の炭素数が異なる複数の化合物の混合物であることが好ましい。また、前記アミノアルコールの製造方法は、例えば、特開２０１３－５４３９２７号に記載されている方法を参照できる。 The method for producing the amino alcohol is not particularly limited. For example, an internal epoxide is synthesized by oxidizing the double bond of the internal olefin with a peroxide such as hydrogen peroxide, performic acid, or peracetic acid, and the obtained internal epoxide can be produced by reacting with a secondary alkanolamine. As the secondary alkanolamine, an alkanolamine having 2 or more and 4 or less hydroxyalkyl groups can be used. Examples of the alkanolamine include N-methylethanolamine, diethanolamine, dipropanolamine, and diisopropanolamine. In addition, the amino alcohol obtained by the production method is preferably a mixture of a plurality of compounds in which the number of carbon atoms in R 1 or R 2 is different. Further, for the method for producing the amino alcohol, for example, the method described in JP-A-2013-543927 can be referred to.
前記アミノアルコールの製造に用いられる内部オレフィンは、末端オレフィンを含有していてもよい。その場合、オレフィン中に含まれる末端オレフィンの含有量は、例えば、０．１質量％以上、０．２質量％以上、また、５質量％以下、３質量％以下、２質量％以下、１質量％以下、０．５質量％以下などである。 The internal olefins used in the production of said aminoalcohols may contain terminal olefins. In that case, the content of the terminal olefin contained in the olefin is, for example, 0.1% by mass or more, 0.2% by mass or more, and 5% by mass or less, 3% by mass or less, 2% by mass or less, and 1% by mass. % or less, or 0.5 mass % or less.
前記油剤添加剤は、前記化学式（１）で表される化合物１種、或いは、前記化学式（１）で表される化合物２種以上の混合物、或いは、これらと原料オレフィンに含まれるオレフィン以外の微量成分及びその誘導体との混合物として得ることができる。 The oil agent additive is a compound represented by the chemical formula (1), or a mixture of two or more compounds represented by the chemical formula (1), or a trace amount of these and other than olefins contained in the raw olefin. It can be obtained as a mixture with components and their derivatives.
前記油剤添加剤は、潤滑油添加剤又は摩擦係数低減剤として好適に使用することができる。 The oil additive can be suitably used as a lubricating oil additive or a friction coefficient reducing agent.
また、前記油剤添加剤は、エンジン又はギアの摩擦係数低減のために好適に使用することができる。 Also, the oil additive can be suitably used for reducing the friction coefficient of the engine or gear.
＜油剤組成物＞
本発明の油剤組成物は、少なくとも油剤と前記油剤添加剤を含有する。
<Oil agent composition>
The oil agent composition of the present invention contains at least an oil agent and the oil agent additive.
前記油剤の融点は、取り扱い容易性の観点から、好ましくは－２００℃以上であり、好ましくは－１５℃以下、より好ましくは－３０℃以下、更に好ましくは－４５℃以下、より更に好ましくは－６０℃以下である。なお、油剤の融点は、高感度型示差走査熱量計（株式会社日立ハイテクサイエンス製、商品名：ＤＳＣ７０００Ｘ）を使用して測定することができる。 From the viewpoint of ease of handling, the melting point of the oil agent is preferably −200° C. or higher, preferably −15° C. or lower, more preferably −30° C. or lower, still more preferably −45° C. or lower, and even more preferably − 60°C or less. The melting point of the oil can be measured using a high-sensitivity differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., trade name: DSC7000X).
前記油剤は、特に制限なく使用可能であり、潤滑性の観点から、好ましくは潤滑油であり、潤滑油としては、例えば、エンジンオイル、及びギア油などが挙げられる。また、前記油剤は、パラフィン系潤滑油であることが好ましい。 The oil agent can be used without any particular limitation, and is preferably a lubricating oil from the viewpoint of lubricity. Examples of the lubricating oil include engine oil and gear oil. Further, the oil agent is preferably a paraffin-based lubricating oil.
前記油剤組成物中の前記油剤添加剤の含有量は特に制限されないが、摩擦係数を低下させる観点から、好ましくは０．０５質量％以上、より好ましくは０．１質量％以上、更に好ましくは０．２質量％以上、より更に好ましくは０．５質量％以上であり、好ましくは２０質量％以下、より好ましくは１０質量％以下、更に好ましくは５質量％以下である。 The content of the oil additive in the oil composition is not particularly limited, but from the viewpoint of lowering the coefficient of friction, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0% by mass. 2% by mass or more, more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
前記油剤組成物は、必要に応じて各種の添加剤を含有してもよい。前記添加剤としては、例えば、酸化防止剤、金属不活性剤、耐摩耗剤、消泡剤、粘度指数向上剤、流動点降下剤、清浄分散剤、防錆剤、及び公知の油剤添加剤などが挙げられる。 The oil composition may contain various additives as necessary. Examples of the additives include antioxidants, metal deactivators, antiwear agents, antifoaming agents, viscosity index improvers, pour point depressants, detergent dispersants, rust inhibitors, and known oil additives. are mentioned.
以下、本発明について、実施例に基づき具体的に説明する。なお、表中に特に示さない限り、各成分の含有量は質量％を示す。また、各種測定方法は以下のとおりである。 EXAMPLES The present invention will be specifically described below based on examples. In addition, unless otherwise indicated in the table, the content of each component indicates % by mass. Moreover, various measuring methods are as follows.
＜内部オレフィンの二重結合位置の測定方法＞
エポキシドジ又はモノエタノールアミン開環体の原料化合物として作製した内部オレフィンの二重結合位置は、ガスクロマトグラフィー（以下、ＧＣと省略）により測定した。具体的には、オレフィンに対しジメチルジスルフィドを反応させることでジチオ化誘導体とした後、各成分をＧＣで分離した。それぞれのピーク面積より内部オレフィンの二重結合位置を求めた。なお、測定に使用した装置及び分析条件は次の通りである。
ＧＣ装置：商品名ＨＰ６８９０（ＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ社製）
カラム：商品名Ｕｌｔｒａ－Ａｌｌｏｙ－１ＨＴキャピラリーカラム３０ｍ×２５０μｍ×０．１５μｍ（フロンティア・ラボ株式会社製）
検出器：水素炎イオン検出器（ＦＩＤ）
インジェクション温度：３００℃
ディテクター温度：３５０℃
オーブン：６０℃（０ｍｉｎ.）→２℃／ｍｉｎ.→２２５℃→２０℃／ｍｉｎ．→３５０℃→３５０℃（５．２ｍｉｎ.）
<Method for Measuring Double Bond Position of Internal Olefin>
The double bond position of the internal olefin prepared as the raw material compound of the epoxide di- or monoethanolamine ring-opening compound was measured by gas chromatography (hereinafter abbreviated as GC). Specifically, the olefin was reacted with dimethyl disulfide to obtain a dithio derivative, and each component was separated by GC. The position of the double bond of the internal olefin was obtained from each peak area. The apparatus and analysis conditions used for measurement are as follows.
GC device: trade name HP6890 (manufactured by HEWLETT PACKARD)
Column: Product name Ultra-Alloy-1HT capillary column 30 m × 250 μm × 0.15 μm (manufactured by Frontier Labs)
Detector: Flame ion detector (FID)
Injection temperature: 300°C
Detector temperature: 350°C
Oven: 60°C (0 min.) → 2°C/min. → 225°C → 20°C/min. → 350°C → 350°C (5.2 min.)
＜構造異性体の含有量比の測定方法＞
実施例及び比較例で製造したエポキシドジ又はモノエタノールアミン開環体０．０５ｇ、トリフルオロ酢酸無水物０．２ｇ、重クロロホルム１ｇを混合し、１Ｈ－ＮＭＲにて測定を行った。測定条件は以下のとおりである。
核磁気共鳴装置：Ａｇｉｌｅｎｔ ４００－ＭＲ ＤＤ２、アジレント・テクノロジー株式会社製
観測範囲：６４１０．３Ｈｚ
データポイント：６５５３６
測定モード：Ｐｒｅｓａｔ
パルス幅：４５°
パルス遅延時間：１０ｓｅｃ
積算回数：１２８回
<Method for measuring content ratio of structural isomers>
0.05 g of the epoxide di- or monoethanolamine ring-opening compound produced in Examples and Comparative Examples, 0.2 g of trifluoroacetic anhydride and 1 g of deuterated chloroform were mixed and measured by 1 H-NMR. The measurement conditions are as follows.
Nuclear magnetic resonance apparatus: Agilent 400-MR DD2, manufactured by Agilent Technologies Inc. Observation range: 6410.3 Hz
Data points: 65536
Measurement mode: Presat
Pulse width: 45°
Pulse delay time: 10 sec
Accumulated times: 128 times
＜内部オレフィンの製造＞
製造例Ａ１
（炭素数１６の内部オレフィン（Ｃ１６内部オレフィン）の製造）
撹拌装置付きフラスコに１－ヘキサデカノール（製品名：カルコール６０９８、花王株式会社製）７０００ｇ（２８．９モル）、固体酸触媒としてγ―アルミナ（ＳＴＲＥＭＣｈｅｍｉｃａｌｓ，Ｉｎｃ社）７００ｇ（原料アルコールに対して１０ｗｔ％）を仕込み、撹拌下、２８０℃にて系内に窒素（７０００ｍＬ／分）を流通させながら３２時間反応を行った。反応終了後のアルコール転化率は１００％、Ｃ１６オレフィン純度は９９．６％であった。得られた粗Ｃ１６内部オレフィンを蒸留器に移し、１３６～１６０℃／４．０ｍｍＨｇで蒸留することでオレフィン純度１００％のＣ１６内部オレフィンを得た。得られたＣ１６内部オレフィンの二重結合分布はＣ１位０．２％、Ｃ２位１５．８％、Ｃ３位１４．５％、Ｃ４位１５．７％、Ｃ５位１７．３％、Ｃ６位１６．５％、Ｃ７位、８位の合計が２０．０％であった。
<Production of internal olefin>
Production example A1
(Production of internal olefin having 16 carbon atoms (C16 internal olefin))
A flask equipped with a stirrer was charged with 7000 g (28.9 mol) of 1-hexadecanol (product name: Calcol 6098, manufactured by Kao Corporation), and 700 g of γ-alumina (STREMC Chemicals, Inc.) as a solid acid catalyst (based on raw material alcohol). 10 wt %) was charged, and the reaction was carried out for 32 hours while nitrogen (7000 mL/min) was passed through the system at 280° C. while stirring. After completion of the reaction, the alcohol conversion rate was 100% and the C16 olefin purity was 99.6%. The resulting crude C16 internal olefin was transferred to a still and distilled at 136-160° C./4.0 mmHg to obtain a C16 internal olefin with an olefin purity of 100%. The resulting C16 internal olefin had a double bond distribution of 0.2% at C1, 15.8% at C2, 14.5% at C3, 15.7% at C4, 17.3% at C5, and 16 at C6. .5%, and the sum of C7 and 8 positions was 20.0%.
製造例Ａ２
（炭素数１８の内部オレフィン（Ｃ１８内部オレフィン）の製造）
撹拌装置付き反応器に１－オクタデカノール（製品名：カルコール８０９８、花王株式会社製）８００ｋｇ（３．０キロモル）、固体酸触媒として活性アルミナＧＰ－２０（水澤化学工業株式会社）８０ｋｇ（原料アルコールに対して１０ｗｔ％）を仕込み、撹拌下、２８０℃にて系内に窒素（１５Ｌ／分）を流通させながら１６時間反応を行った。反応終了後のアルコール転化率は１００％、Ｃ１８オレフィン純度は９８．７％であった。得られた粗Ｃ１８内部オレフィンを蒸留器に移し、１６３～１９０℃／４．６ｍｍＨｇで蒸留することでオレフィン純度１００％のＣ１８内部オレフィンを得た。得られたＣ１８内部オレフィンの二重結合分布はＣ１位０．３％、Ｃ２位１３．３％、Ｃ３位１２．６％、Ｃ４位１３．９％、Ｃ５位１４．８％、Ｃ６位１３．７％、Ｃ７位１２．６、Ｃ８位、９位の合計が１８．８％であった。
Production example A2
(Production of internal olefin having 18 carbon atoms (C18 internal olefin))
800 kg (3.0 kmol) of 1-octadecanol (product name: Calcol 8098, manufactured by Kao Corporation) was added to a reactor equipped with a stirrer, and 80 kg of activated alumina GP-20 (Mizusawa Chemical Industry Co., Ltd.) as a solid acid catalyst (raw material). 10 wt % with respect to the alcohol), and under stirring, the reaction was carried out for 16 hours at 280° C. while circulating nitrogen (15 L/min) in the system. After completion of the reaction, the alcohol conversion rate was 100% and the C18 olefin purity was 98.7%. The resulting crude C18 internal olefin was transferred to a still and distilled at 163-190° C./4.6 mmHg to obtain C18 internal olefin with an olefin purity of 100%. The resulting C18 internal olefin has a double bond distribution of 0.3% at C1, 13.3% at C2, 12.6% at C3, 13.9% at C4, 14.8% at C5, and 13 at C6. .7%, C7 position 12.6, C8 position, 9 position total 18.8%.
＜内部エポキシドの製造＞
製造例Ｂ１
（炭素数１６の内部エポキシド（Ｃ１６内部エポキシド）の製造）
撹拌装置付きフラスコに製造例Ａ１で得たＣ１６内部オレフィン（８００ｇ、３．５６モル）、酢酸（富士フイルム和光純薬工業株式会社製）１０７ｇ（１．７８モル）、硫酸（富士フイルム和光純薬工業株式会社製）１５．６ｇ（０．１５モル）、３５％過酸化水素（富士フイルム和光純薬工業株式会社製）４１５．７ｇ（４．２８モル）、硫酸ナトリウム（富士フイルム和光純薬工業株式会社製）２５．３ｇ（０．１８モル）を仕込み、５０℃で４時間反応した。その後、７０℃に昇温し更に２時間反応を行った。反応後、分層して水層を抜出し、油層をイオン交換水、飽和炭酸ナトリウム水溶液（富士フイルム和光純薬工業株式会社製）、飽和亜硫酸ナトリウム水溶液（富士フイルム和光純薬工業株式会社製）、１％食塩水（富士フイルム和光純薬工業株式会社製）にて洗浄を行いエバポレーターにて濃縮し、Ｃ１６内部エポキシドを８２０ｇ得た。
<Production of internal epoxide>
Production example B1
(Production of internal epoxide having 16 carbon atoms (C16 internal epoxide))
C16 internal olefin obtained in Production Example A1 (800 g, 3.56 mol), acetic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 107 g (1.78 mol), sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a flask equipped with a stirrer. Industry Co., Ltd.) 15.6 g (0.15 mol), 35% hydrogen peroxide (FUJIFILM Wako Pure Chemical Industries, Ltd.) 415.7 g (4.28 mol), sodium sulfate (FUJIFILM Wako Pure Chemical Industries, Ltd.) 25.3 g (0.18 mol) of the product manufactured by Co., Ltd. was charged and reacted at 50° C. for 4 hours. After that, the temperature was raised to 70° C. and the reaction was further carried out for 2 hours. After the reaction, the layers are separated and the aqueous layer is extracted, and the oil layer is deionized water, saturated sodium carbonate aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), saturated sodium sulfite aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), After washing with a 1% saline solution (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and concentrating with an evaporator, 820 g of C16 internal epoxide was obtained.
製造例Ｂ２
（炭素数１８の内部エポキシド（Ｃ１８内部エポキシド）の製造）
撹拌装置付きフラスコに製造例Ａ２で得たＣ１８内部オレフィン（５９５ｇ、２．３８モル）、酢酸（富士フイルム和光純薬株式会社製）７１．７ｇ（１．２０モル）、硫酸（富士フイルム和光純薬株式会社製）９．８ｇ（０．１０モル）、３５％過酸化水素（富士フイルム和光純薬株式会社製）３２４ｇ（４．００モル）を仕込み、５０℃で４時間反応した。その後、８０℃に昇温し更に５時間反応を行った。反応後、分層して水層を抜出し、油層をイオン交換水、飽和炭酸ナトリウム水溶液（富士フイルム和光純薬株式会社製）、飽和亜硫酸ナトリウム水溶液（富士フイルム和光純薬株式会社製）、イオン交換水にて洗浄を行いエバポレーターにて濃縮し、Ｃ１８内部エポキシドを６２９ｇ得た。
Production example B2
(Production of C18 internal epoxide (C18 internal epoxide))
C18 internal olefin obtained in Production Example A2 (595 g, 2.38 mol), acetic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 71.7 g (1.20 mol), sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a flask equipped with a stirring device. Yaku Co., Ltd.) and 324 g (4.00 mol) of 35% hydrogen peroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were charged and reacted at 50° C. for 4 hours. After that, the temperature was raised to 80° C. and the reaction was further carried out for 5 hours. After the reaction, the layers are separated and the aqueous layer is extracted, and the oil layer is treated with deionized water, saturated sodium carbonate aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), saturated sodium sulfite aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and ion exchange. After washing with water and concentrating with an evaporator, 629 g of C18 internal epoxide was obtained.
＜内部エポキシドとジ又はモノエタノールアミンの反応物（油剤添加剤）の製造＞
製造例Ｃ１（油剤添加剤１）
撹拌装置付きフラスコに製造例Ｂ１で得たＣ１６内部エポキシド（４００ｇ、１．６６モル）、ジエタノールアミン（富士フイルム和光純薬株式会社製）５２５ｇ（４．９９モル）を仕込み１６０℃に昇温し、２０時間反応を行った。この反応により得られた液にヘキサンを加えイオン交換水にて水洗を行った後、エバポレーターにて減圧濃縮を行い、内部エポキシドジエタノールアミン開環体であるアミノアルコール（油剤添加剤１）を５７０ｇ得た。得られた油剤添加剤１は、前記化学式（１）において、Ｒ１及びＲ２はそれぞれ炭素数１～１３のアルキル基を含み、Ｒ１とＲ２の合計炭素数が１４、Ｘが単結合であり、Ｒ３が炭素数２のヒドロキシエチル基、Ｒ４が炭素数２のヒドロキシエチル基である。また、Ｒ１の炭素数が５以上かつＲ２の炭素数が５以上の化合物の含有割合が、原料に用いた内部オレフィンの二重結合分布から３６．５質量％と推定された。
<Production of Reaction Product (Oil Agent Additive) of Internal Epoxide and Di- or Monoethanolamine>
Production Example C1 (oil additive 1)
C16 internal epoxide (400 g, 1.66 mol) obtained in Production Example B1 and 525 g (4.99 mol) of diethanolamine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were placed in a flask equipped with a stirrer and heated to 160°C. The reaction was carried out for 20 hours. Hexane was added to the liquid obtained by this reaction, washed with deionized water, and then concentrated under reduced pressure using an evaporator to obtain 570 g of aminoalcohol (lubricant additive 1), which is an internal epoxide diethanolamine ring-opening compound. . The resulting oil additive 1 has the chemical formula (1) wherein R 1 and R 2 each contain an alkyl group having 1 to 13 carbon atoms, the total number of carbon atoms of R 1 and R 2 is 14, and X is a single bond. wherein R 3 is a hydroxyethyl group having 2 carbon atoms and R 4 is a hydroxyethyl group having 2 carbon atoms. Also, the content of compounds in which R 1 has 5 or more carbon atoms and R 2 has 5 or more carbon atoms was estimated to be 36.5% by mass from the double bond distribution of the internal olefin used as the raw material.
製造例Ｃ２（油剤添加剤２）
撹拌装置付きフラスコに製造例Ｂ２で得たＣ１８内部エポキシド（４００ｇ、１．４９モル）、ジエタノールアミン（富士フイルム和光純薬株式会社製）４７０ｇ（４．４７モル）を仕込み１６０℃に昇温し、２０時間反応を行った。この反応により得られた液にヘキサンを加えイオン交換水にて水洗を行った後、エバポレーターにて減圧濃縮を行い、内部エポキシドジエタノールアミン開環体であるアミノアルコール（油剤添加剤２）を５３０ｇ得た。得られた油剤添加剤２は、前記化学式（１）において、Ｒ１及びＲ２はそれぞれ炭素数１～１５のアルキル基を含み、Ｒ１とＲ２の合計炭素数が１６、Ｘが単結合であり、Ｒ３が炭素数２のヒドロキシエチル基、Ｒ４が炭素数２のヒドロキシエチル基である。また、Ｒ１の炭素数が５以上かつＲ２の炭素数が５以上の化合物の含有割合が、原料に用いた内部オレフィンの二重結合分布から４５質量％と推定された。
Production Example C2 (oil additive 2)
A flask equipped with a stirrer was charged with the C18 internal epoxide (400 g, 1.49 mol) obtained in Production Example B2 and 470 g (4.47 mol) of diethanolamine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and the temperature was raised to 160°C. The reaction was carried out for 20 hours. Hexane was added to the liquid obtained by this reaction, washed with deionized water, and then concentrated under reduced pressure using an evaporator to obtain 530 g of aminoalcohol (lubricant additive 2), which is an internal epoxide diethanolamine ring-opening compound. . The resulting oil additive 2 has the chemical formula (1) wherein R 1 and R 2 each contain an alkyl group having 1 to 15 carbon atoms, the total number of carbon atoms of R 1 and R 2 is 16, and X is a single bond. wherein R 3 is a hydroxyethyl group having 2 carbon atoms and R 4 is a hydroxyethyl group having 2 carbon atoms. In addition, the content of compounds in which R 1 has 5 or more carbon atoms and R 2 has 5 or more carbon atoms was estimated to be 45% by mass from the double bond distribution of the internal olefin used as the raw material.
製造例Ｃ３（油剤添加剤３）
撹拌装置付きフラスコに製造例Ｂ２で得たＣ１８内部エポキシド（５００ｇ、１．８６モル）、モノエタノールアミン（富士フイルム和光純薬株式会社製）３４１ｇ（５．５９モル）を仕込み１４０℃に昇温し、８時間反応を行った。この反応により得られた液にヘキサンを加えイオン交換水にて水洗を行った後、エバポレーターにて減圧濃縮を行い、内部エポキシドモノエタノールアミン開環体であるアミノアルコール（油剤添加剤３）を６００ｇ得た。得られた油剤添加剤３は、前記化学式（１）において、Ｒ１及びＲ２はそれぞれ炭素数１～１５のアルキル基を含み、Ｒ１とＲ２の合計炭素数が１６、Ｘが単結合であり、Ｒ３が水素原子、Ｒ４が炭素数２のヒドロキシエチル基である。また、Ｒ１の炭素数が５以上かつＲ２の炭素数が５以上の化合物の含有割合が、原料に用いた内部オレフィンの二重結合分布から４５質量％と推定された。
Production Example C3 (oil additive 3)
C18 internal epoxide (500 g, 1.86 mol) obtained in Production Example B2 and 341 g (5.59 mol) of monoethanolamine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were placed in a flask equipped with a stirrer and heated to 140°C. and reacted for 8 hours. Hexane was added to the liquid obtained by this reaction, washed with deionized water, and then concentrated under reduced pressure using an evaporator. Obtained. The resulting oil additive 3 has the chemical formula (1), wherein each of R 1 and R 2 contains an alkyl group having 1 to 15 carbon atoms, the total number of carbon atoms of R 1 and R 2 is 16, and X is a single bond. where R 3 is a hydrogen atom and R 4 is a hydroxyethyl group having 2 carbon atoms. In addition, the content of compounds in which R 1 has 5 or more carbon atoms and R 2 has 5 or more carbon atoms was estimated to be 45% by mass from the double bond distribution of the internal olefin used as the raw material.
＜油剤添加剤の融点の測定＞
高感度型示差走査熱量計（株式会社日立ハイテクサイエンス製、商品名：ＤＳＣ７０００Ｘ）を使用し、７０μＬパンに各油剤添加剤を入れ、－６０℃から８０℃まで１℃／ｍｉｎで昇温し、昇温時間に対する示差熱電極で検出する温度差の最大ピーク時の温度を融点とした。測定結果を表１に示す。
<Measurement of melting point of oil additive>
Using a high-sensitivity differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., product name: DSC7000X), each oil additive was placed in a 70 μL pan, and the temperature was raised from -60 ° C. to 80 ° C. at 1 ° C./min. The temperature at the maximum peak of the temperature difference detected by the differential thermal electrode with respect to the heating time was taken as the melting point. Table 1 shows the measurement results.
実施例１～１４、比較例１～８
表１に記載の油剤に、表１に記載の油剤添加剤（製造例Ｃ１～Ｃ３で作製した油剤添加剤１～３）を表１に記載の添加量で添加し、８０℃で十分に混合して油剤組成物を調製した。なお、表１に記載の油剤は以下の通りである。
＜油剤＞
油剤１：鉱油 コスモニュートラル１５０
油剤２：エンジンオイル ＳＵＳＴＩＮＡ ０Ｗ－２０
Examples 1-14, Comparative Examples 1-8
To the oil described in Table 1, the oil additive described in Table 1 (oil additive 1 to 3 produced in Production Examples C1 to C3) was added in the amount described in Table 1, and thoroughly mixed at 80°C. Then, an oil composition was prepared. The oils shown in Table 1 are as follows.
<Oil solution>
Oil agent 1: Mineral oil Cosmo Neutral 150
Lubricant 2: Engine oil SUSTINA 0W-20
実施例及び比較例で調製した油剤組成物を用いて、摩擦係数の測定を行った。
＜摩擦係数の測定＞
ＭＴＭ２トラクション計測器（ＰＣＳ Ｉｎｓｔｒｕｍｅｎｔｓ Ｌｔｄ．社製）を用いて、下記に示す測定条件にて、調製した各油剤組成物の摩擦係数を測定した。結果を表１に示す。摩擦係数が小さいほど、省燃費性に優れているといえる。
測定条件
負荷荷重：５０Ｎ
油温：８０℃又は１２０℃
スライド・ロールレシオ：５０％
平均回転速度：１０ｍｍ／ｓ又は１００ｍｍ／ｓ
Friction coefficients were measured using the oil compositions prepared in Examples and Comparative Examples.
<Measurement of friction coefficient>
Using an MTM2 traction measuring instrument (manufactured by PCS Instruments Ltd.), the friction coefficient of each prepared oil composition was measured under the following measurement conditions. Table 1 shows the results. It can be said that the smaller the coefficient of friction, the better the fuel economy.
Measurement conditions Applied load: 50N
Oil temperature: 80°C or 120°C
Slide/roll ratio: 50%
Average rotation speed: 10mm/s or 100mm/s
本発明の油剤添加剤は、各種の油剤組成物に添加される摩擦低減剤として有用である。
The oil additive of the present invention is useful as a friction reducing agent added to various oil compositions.
Claims (13)
Use of the oil additive according to any one of claims 1 to 5 for reducing the friction coefficient of an engine or gear.
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