JP6113004B2 - Poly (meth) acrylate viscosity index improver, and lubricating oil additive and lubricating oil composition containing the viscosity index improver - Google Patents
Poly (meth) acrylate viscosity index improver, and lubricating oil additive and lubricating oil composition containing the viscosity index improver Download PDFInfo
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- JP6113004B2 JP6113004B2 JP2013142021A JP2013142021A JP6113004B2 JP 6113004 B2 JP6113004 B2 JP 6113004B2 JP 2013142021 A JP2013142021 A JP 2013142021A JP 2013142021 A JP2013142021 A JP 2013142021A JP 6113004 B2 JP6113004 B2 JP 6113004B2
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- viscosity index
- meth
- index improver
- lubricating oil
- poly
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- 239000010687 lubricating oil Substances 0.000 title claims description 52
- 229920000193 polymethacrylate Polymers 0.000 title claims description 51
- 239000000203 mixture Substances 0.000 title claims description 28
- 239000000654 additive Substances 0.000 title claims description 27
- 230000000996 additive effect Effects 0.000 title claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000002199 base oil Substances 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 230000001050 lubricating effect Effects 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 14
- -1 (3-methyl-4-hydroxy) -5-tert-butylbenzyl Chemical group 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002480 mineral oil Substances 0.000 description 13
- 235000010446 mineral oil Nutrition 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000003999 initiator Substances 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 10
- 239000000446 fuel Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 239000002685 polymerization catalyst Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- VGUWFGWZSVLROP-UHFFFAOYSA-N 1-pyridin-2-yl-n,n-bis(pyridin-2-ylmethyl)methanamine Chemical compound C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CC1=CC=CC=N1 VGUWFGWZSVLROP-UHFFFAOYSA-N 0.000 description 4
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- XXSPGBOGLXKMDU-UHFFFAOYSA-M 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C([O-])=O XXSPGBOGLXKMDU-UHFFFAOYSA-M 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000009849 vacuum degassing Methods 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- UEBFCIQDWYULRW-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;2-bromo-2-methylpropanoic acid Chemical compound CC(C)(Br)C(O)=O.CC(C)(Br)C(O)=O.CC(C)(Br)C(O)=O.CC(C)(Br)C(O)=O.OCC(CO)(CO)CO UEBFCIQDWYULRW-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- PQFFVPSTVLFQPD-UHFFFAOYSA-N 2-bromo-2-methyl-1-prop-1-enoxypropane Chemical compound BrC(COC=CC)(C)C PQFFVPSTVLFQPD-UHFFFAOYSA-N 0.000 description 2
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VLRDGSDXAISNJF-UHFFFAOYSA-N [3-(2-bromo-2-methylpropanoyl)oxy-2-[(2-bromo-2-methylpropanoyl)oxymethyl]-2-methylpropyl] 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C(=O)OCC(C)(COC(=O)C(C)(C)Br)COC(=O)C(C)(C)Br VLRDGSDXAISNJF-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 2
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- 238000010008 shearing Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
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- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical compound C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 description 1
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- GSOYMOAPJZYXTB-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 GSOYMOAPJZYXTB-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
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- CWTQBXKJKDAOSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;octanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC(O)=O CWTQBXKJKDAOSQ-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、ポリ（メタ）アクリレート系粘度指数向上剤、並びに該粘度指数向上剤を含有する潤滑油添加剤及び潤滑油組成物に関する。 The present invention relates to a poly (meth) acrylate viscosity index improver, and a lubricating oil additive and a lubricating oil composition containing the viscosity index improver.
従来、潤滑油の分野では、省エネルギー性の観点から潤滑油の改良が検討されている。特に近年は、地球環境保護の気運が高まり、潤滑油に対する省エネルギー性改善効果の要求は一層強まっている。 Conventionally, in the field of lubricating oil, improvement of lubricating oil has been studied from the viewpoint of energy saving. In particular, in recent years, the trend of protecting the global environment has increased, and the demand for an energy saving improvement effect on lubricating oil has become even stronger.
例えば、自動車の変速機に用いられるＡＴＦ、ＭＴＦ、ＣＶＴＦ等の潤滑油（「変速機用潤滑油」又は「駆動系油」とも呼ばれる。）の場合、省燃費性を改善する手段の一つとして、変速機用潤滑油を低粘度化して粘性抵抗を低減する方法が挙げられる。しかし、変速機用潤滑油を低粘度化すると、油漏れ、焼付きなどの別の問題が生じるおそれがある。 For example, in the case of lubricating oils such as ATF, MTF, CVTF, etc. (also referred to as “transmission lubricating oil” or “driving system oil”) used in automobile transmissions, as one means for improving fuel efficiency. And a method of reducing viscosity resistance by reducing the viscosity of transmission lubricating oil. However, when the viscosity of the transmission lubricating oil is lowered, other problems such as oil leakage and seizure may occur.
そこで、省燃費性を改善する他の方法として、粘度指数向上剤を用いる方法がある。この方法は、粘度指数向上剤を用いることによって変速機用潤滑油の粘度指数を高くし、高温領域での粘度を維持しつつ、低温領域での粘度増加を抑制するものである。粘度指数向上剤については、これまで各種の粘度指数向上剤の使用が提案されているが、特にポリ（メタ）クリレート系粘度指数向上剤の使用が多く提案されている（例えば特許文献１〜７参照）。 Therefore, as another method for improving fuel economy, there is a method using a viscosity index improver. In this method, the viscosity index of the transmission lubricant is increased by using a viscosity index improver, and the increase in the viscosity in the low temperature region is suppressed while the viscosity in the high temperature region is maintained. Regarding the viscosity index improver, various types of viscosity index improvers have been proposed so far, but in particular, the use of poly (meth) acrylate viscosity index improvers has been proposed (for example, Patent Documents 1 to 7). reference).
ところで、省燃費性が悪化する原因の一つとして、駆動装置内にある歯車の動力伝達時の摩擦損失が挙げられる。したがって、高せん断条件下で粘性抵抗の低い潤滑油を実現できれば、摩擦損失を低減することができ、省燃費性をさらに向上させることができる。しかし、上述した従来の粘度指数向上剤は、高粘度指数化により高温領域及び低温領域の粘度特性の改善を図るものであり、摩擦損失低減効果の点では十分とはいえない。 By the way, as one of the causes of the deterioration of fuel efficiency, there is a friction loss at the time of power transmission of a gear in the drive device. Therefore, if a lubricating oil with low viscous resistance can be realized under high shear conditions, friction loss can be reduced and fuel economy can be further improved. However, the above-described conventional viscosity index improvers improve the viscosity characteristics in the high temperature region and the low temperature region by increasing the viscosity index, and are not sufficient in terms of the effect of reducing friction loss.
さらに、駆動系油はほとんど交換することがないため、省燃費の持続性が求められている。省燃費持続性には、粘度指数向上剤のせん断安定性が大きく影響するため、粘度指数向上剤としては、摩擦損失低減効果に加えてせん断安定性に優れることが望ましい。しかし、従来のポリ（メタ）アクリレート系粘度指数向上剤は、摩擦損失低減効果とせん断安定性との両立の点でも十分であるとはいえない。 Furthermore, since drive system oil is hardly changed, the sustainability of a fuel-saving is calculated | required. Since the shear stability of the viscosity index improver greatly affects the fuel economy, it is desirable that the viscosity index improver be excellent in shear stability in addition to the effect of reducing friction loss. However, it cannot be said that the conventional poly (meth) acrylate viscosity index improver is sufficient in terms of both the friction loss reducing effect and the shear stability.
そこで、本発明は、十分な摩擦損失低減効果を潤滑油に付与することができ、せん断安定性に優れる粘度指数向上剤、並びに該粘度指数向上剤を含有する潤滑油添加剤及び潤滑油組成物を提供することを目的とする。 Accordingly, the present invention can provide a lubricating oil with a sufficient friction loss reducing effect and is excellent in shear stability, and a lubricating oil additive and a lubricating oil composition containing the viscosity index improving agent. The purpose is to provide.
本発明者らは、鋭意検討した結果、特定の構造を有し、重量平均分子量、及び重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎが特定の条件を満たすポリ（メタ）アクリレート系粘度指数向上剤が、摩擦損失低減効果を付与することができ、せん断安定性に優れることを見出し、本発明を完成するに至った。 As a result of intensive studies, the inventors of the present invention have a specific structure, and a poly (meth) acrylate system having a weight average molecular weight and a ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn satisfying a specific condition. It has been found that the viscosity index improver can impart a friction loss reducing effect and is excellent in shear stability, and the present invention has been completed.
すなわち、本発明は、コア部と、下記一般式（１）で表される構造単位を含む重合鎖からなり且つ該重合鎖の一端がコア部に結合しているアーム部の３つ以上と、を有し、重量平均分子量Ｍｗが１００，０００未満であり、重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎが１．６以下である、ポリ（メタ）アクリレート系粘度指数向上剤を提供する。
［式（１）中、Ｒ１は水素又はメチル基を示し、Ｒ２は炭素数１以上３６以下のアルキル基を示す。］
That is, the present invention comprises a core part and three or more arm parts each composed of a polymer chain containing a structural unit represented by the following general formula (1) and having one end of the polymer chain bonded to the core part; A poly (meth) acrylate viscosity index improver having a weight average molecular weight Mw of less than 100,000 and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 1.6 or less. provide.
[In Formula (1), R 1 represents hydrogen or a methyl group, and R 2 represents an alkyl group having 1 to 36 carbon atoms. ]
また、本発明は、上記ポリ（メタ）アクリレート系粘度指数向上剤を含有する潤滑油添加剤を提供する。 Moreover, this invention provides the lubricating oil additive containing the said poly (meth) acrylate type viscosity index improver.
また、本発明は、潤滑油基油と、上記ポリ（メタ）アクリレート系粘度指数向上剤を含有する潤滑油組成物を提供する。 The present invention also provides a lubricating oil composition comprising a lubricating base oil and the poly (meth) acrylate viscosity index improver.
本発明によれば、十分な摩擦損失低減効果を潤滑油に付与することができ、せん断安定性に優れる粘度指数向上剤、並びに該粘度指数向上剤を含有する潤滑油添加剤及び潤滑油組成物を提供することができる。 According to the present invention, a sufficient viscosity loss reducing effect can be imparted to a lubricating oil, and a viscosity index improver excellent in shear stability, and a lubricating oil additive and a lubricating oil composition containing the viscosity index improver Can be provided.
以下、本発明の好適な実施形態について詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.
［第１実施形態：ポリ（メタ）アクリレート系粘度指数向上剤］
第１実施形態に係るポリ（メタ）アクリレート系粘度指数向上剤は、コア部と、下記一般式（１）で表される構造単位を含む重合鎖からなり且つ重合鎖の一端がコア部に結合しているアーム部の３つ以上と、を有する。該ポリ（メタ）アクリレート系粘度指数向上剤の重量平均分子量Ｍｗ（以下、場合により単に「Ｍｗ」という。）は１００，０００未満であり、重量平均分子量Ｍｗと数平均分子量Ｍｎ（以下、場合により単に「Ｍｗ」という。）との比Ｍｗ／Ｍｎ（以下、場合により単に「Ｍｗ／Ｍｎ」という。）は１．６以下である。
[First Embodiment: Poly (meth) acrylate viscosity index improver]
The poly (meth) acrylate viscosity index improver according to the first embodiment includes a core part and a polymer chain containing a structural unit represented by the following general formula (1), and one end of the polymer chain is bonded to the core part. And at least three arm portions. The poly (meth) acrylate viscosity index improver has a weight average molecular weight Mw (hereinafter, simply referred to as “Mw” in some cases) of less than 100,000, and a weight average molecular weight Mw and a number average molecular weight Mn (hereinafter, depending on circumstances). The ratio Mw / Mn (hereinafter simply referred to as “Mw / Mn”) is 1.6 or less.
［式（１）中、Ｒ１は水素又はメチル基を示し、Ｒ２は炭素数１以上３６以下のアルキル基を示す。］
[In Formula (1), R 1 represents hydrogen or a methyl group, and R 2 represents an alkyl group having 1 to 36 carbon atoms. ]
Ｒ１は水素又はメチル基のいずれであってもよいが、好ましくはメチル基である。 R 1 may be either hydrogen or a methyl group, but is preferably a methyl group.
Ｒ２で示されるアルキル基の炭素数は、上記のとおり１以上３６以下であり、取扱性及び製造容易性の観点から、１〜３０であることが好ましく、１〜２６であることがより好ましく、１〜２２であることが更に好ましい。また、Ｒ２で示されるアルキル基は、直鎖状であっても、分岐状であってもよい。 The number of carbon atoms of the alkyl group represented by R 2 is 1 or more and 36 or less as described above, and is preferably 1 to 30 and more preferably 1 to 26 from the viewpoints of handleability and manufacturability. 1 to 22 is more preferable. Further, the alkyl group represented by R 2 may be linear or branched.
重合鎖に含まれる上記一般式（１）で表される構造単位が２以上の場合、Ｒ１及びＲ２は構造単位同士で同一でも異なっていてもよい。Ｒ２の異なる２種以上の構造単位が含まれる場合、粘度温度特性の観点から、Ｒ２がメチル基である構造単位が、重合鎖に含まれる構造単位の全量を基準として、１０〜４５質量％含まれることが好ましく、１５〜４５質量％含まれることがより好ましく、２０〜４５質量％含まれることが更に好ましい。また、省燃費特性の観点から、Ｒ２が炭素数１８以上のアルキル基である構造単位が、重合鎖に含まれる構造単位の全量を基準として、１０質量％以上含まれることが好ましく、１５質量％以上含まれることがより好ましく、２０質量％以上含まれることが更に好ましい。 When the structural unit represented by the general formula (1) contained in the polymer chain is 2 or more, R 1 and R 2 may be the same or different among the structural units. When two or more types of structural units different in R 2 are contained, from the viewpoint of viscosity temperature characteristics, the structural unit in which R 2 is a methyl group is 10 to 45 masses based on the total amount of structural units contained in the polymer chain. %, Preferably 15 to 45% by mass, more preferably 20 to 45% by mass. From the viewpoint of fuel saving properties, it is preferable that the structural unit in which R 2 is an alkyl group having 18 or more carbon atoms is contained in an amount of 10% by mass or more based on the total amount of structural units contained in the polymer chain, % Or more is more preferable, and 20% by mass or more is more preferable.
重合鎖は、上記一般式（１）で表される構造単位のみを含んでいてもよく、あるいは、上記一般式（１）で表される構造単位の他に、上記一般式（１）で表される構造単位以外の構造単位を更に含んでいてもよい。また、重合鎖の末端のうち、一端はコア部に結合しており、他端については結合する原子に特に制限はない。このような重合鎖の中でも、上記一般式（１）で表される構造単位のみを含んでおり、一端がコア部に結合し、他端が水素原子に結合している重合鎖、すなわち下記一般式（２）で表される重合鎖であることが好ましい。 The polymer chain may contain only the structural unit represented by the general formula (1), or represented by the general formula (1) in addition to the structural unit represented by the general formula (1). A structural unit other than the structural unit to be formed may be further included. Moreover, one end is couple | bonded with the core part among the terminals of a polymer chain, and there is no restriction | limiting in particular in the atom couple | bonded about the other end. Among such polymer chains, a polymer chain containing only the structural unit represented by the general formula (1), one end bonded to the core portion and the other end bonded to a hydrogen atom, that is, the following general chain A polymer chain represented by the formula (2) is preferable.
式（２）中、Ｒ１は水素又はメチル基を示し、Ｒ２は炭素数１以上３６以下のアルキル基を示し、ｎはポリ（メタ）アクリレート系粘度指数向上剤のＭｗ及びＭｗ／Ｍｎが上記の条件を満たすように選ばれる整数である。ｎは、例えば４０〜４５０の整数である。また、＊はコア部との結合手を示す。 In Formula (2), R 1 represents hydrogen or a methyl group, R 2 represents an alkyl group having 1 to 36 carbon atoms, and n represents Mw and Mw / Mn of the poly (meth) acrylate viscosity index improver. It is an integer chosen to satisfy the above conditions. n is an integer of 40 to 450, for example. Moreover, * shows the joint with a core part.
アーム部１つあたりの重量平均分子量Ｍｗは、ポリ（メタ）アクリレート系粘度指数向上剤のＭｗが上記の条件を満たすように適宜選ばれるが、３３，０００以下であることが好ましく、３０，０００以下であることがより好ましく、２７，０００以下であることが更に好ましい。 The weight average molecular weight Mw per arm is appropriately selected so that the Mw of the poly (meth) acrylate viscosity index improver satisfies the above-mentioned conditions, but is preferably 33,000 or less, and 30,000. Or less, more preferably 27,000 or less.
アーム部１つあたりの数平均分子量Ｍｎは、ポリ（メタ）アクリレート系粘度指数向上剤のＭｗ／Ｍｎが上記の条件を満たすように適宜選ばれるが、２，０００以上であることが好ましく、４，０００以上であることがより好ましく、８，０００以上であることが更に好ましい。 The number average molecular weight Mn per arm is appropriately selected so that the Mw / Mn of the poly (meth) acrylate viscosity index improver satisfies the above-mentioned conditions, but is preferably 2,000 or more. Is more preferably 8,000 or more, and further preferably 8,000 or more.
ポリ（メタ）アクリレート系粘度指数向上剤の重量平均分子量Ｍｗは、１００，０００未満であり、せん断安定性の観点から、９０，０００以下であることが好ましく、８０，０００以下であることがより好ましく、６０，０００以下であることが更に好ましい。Ｍｗの下限は特に制限されないが、Ｍｗは例えば１０，０００以上である。 The weight average molecular weight Mw of the poly (meth) acrylate viscosity index improver is less than 100,000, and is preferably 90,000 or less, more preferably 80,000 or less, from the viewpoint of shear stability. Preferably, it is 60,000 or less. The lower limit of Mw is not particularly limited, but Mw is, for example, 10,000 or more.
ポリ（メタ）アクリレート系粘度指数向上剤の重量平均分子量Ｍｗは、１００，０００未満であり、せん断安定性の観点から、９０，０００以下であることが好ましく、８０，０００以下であることがより好ましく、６０，０００以下であることが更に好ましい。Ｍｗの下限は特に制限されないが、Ｍｗは例えば１０，０００以上である。 The weight average molecular weight Mw of the poly (meth) acrylate viscosity index improver is less than 100,000, and is preferably 90,000 or less, more preferably 80,000 or less, from the viewpoint of shear stability. Preferably, it is 60,000 or less. The lower limit of Mw is not particularly limited, but Mw is, for example, 10,000 or more.
ポリ（メタ）アクリレート系粘度指数向上剤の数平均分子量Ｍｎは、Ｍｗ／Ｍｎが上記の条件を満たすように適宜選択される。Ｍｎは、省燃費特性の観点から、６，０００以上であることが好ましく、１０，０００以上であることがより好ましく、１２，５００以上であることが更に好ましい。Ｍｎの上限は特に制限されないが、Ｍｎは例えば６０，０００以下である。 The number average molecular weight Mn of the poly (meth) acrylate viscosity index improver is appropriately selected so that Mw / Mn satisfies the above conditions. Mn is preferably 6,000 or more, more preferably 10,000 or more, and further preferably 12,500 or more, from the viewpoint of fuel saving characteristics. The upper limit of Mn is not particularly limited, but Mn is, for example, 60,000 or less.
なお、本発明でいう「重量平均分子量Ｍｗ」、「数平均分子量Ｍｎ」及び「重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎ」とは、ＧＰＣ分析により得られるＭｗ、Ｍｎ及びＭｗ／Ｍｎ（ポリスチレン（標準試料）換算値）を意味する。ポリ（メタ）アクリレート系粘度指数向上剤のＭｗ／Ｍｎ及びアーム部１つあたりのＭｗ及びＭｎは、例えば以下のように測定することができる。 In the present invention, “weight average molecular weight Mw”, “number average molecular weight Mn” and “ratio Mw / Mn of weight average molecular weight Mw and number average molecular weight Mn” are Mw, Mn and Mw obtained by GPC analysis. / Mn (polystyrene (standard sample) conversion value). Mw / Mn of the poly (meth) acrylate viscosity index improver and Mw and Mn per arm part can be measured, for example, as follows.
溶剤としてテトラヒドロフランを使用し、希釈して試料濃度を２質量％とした溶液を調製する。その試料溶液を、ＧＰＣ装置（Ｗａｔｅｒｓ Ａｌｌｉａｎｃｅ２６９５）を用いて分析を行う。溶剤の流速は１ｍｌ／ｍｉｎ、分析可能分子量１０，０００から２５６，０００のカラムを使用し、屈折率を検出器として分析を実施する。なお、分子量が明確なポリスチレン標準を用いてカラム保持時間と分子量との関係を求め、検量線を別途作成した上で、得られた保持時間から分子量を決定する。得られた分子量（ＭｗとＭｎ）と開始剤の官能基数で割ることでアームの分子量（ＭｗとＭｎ）を算出することができる。 Tetrahydrofuran is used as a solvent and diluted to prepare a solution with a sample concentration of 2% by mass. The sample solution is analyzed using a GPC apparatus (Waters Alliance 2695). The analysis is carried out using a column having a solvent flow rate of 1 ml / min, an analyzable molecular weight of 10,000 to 256,000, and a refractive index as a detector. The relationship between the column retention time and the molecular weight is determined using a polystyrene standard with a clear molecular weight, a calibration curve is separately prepared, and the molecular weight is determined from the obtained retention time. The molecular weight of the arm (Mw and Mn) can be calculated by dividing the obtained molecular weight (Mw and Mn) by the number of functional groups of the initiator.
コア部は、アクリロイル基の炭素−炭素二重結合と反応する官能基を３つ以上有する化合物に由来するものである。アクリロイル基の炭素−炭素二重結合と反応する官能基を３つ以上有する化合物としては、例えば、１，１，１−トリス（２−ブロモイソブチルオキシメチレン）エタン、ペンタエリスリトールテトラキス（２−ブロモイソブチレート）、ジペンタエリスリトールヘキサキス（２−ブロモイソブチレート）が挙げられる。 The core portion is derived from a compound having three or more functional groups that react with the carbon-carbon double bond of the acryloyl group. Examples of the compound having three or more functional groups that react with the carbon-carbon double bond of the acryloyl group include 1,1,1-tris (2-bromoisobutyloxymethylene) ethane, pentaerythritol tetrakis (2-bromoiso). Butyrate) and dipentaerythritol hexakis (2-bromoisobutyrate).
ポリ（メタ）アクリレート系粘度指数向上剤が有するアーム部の数は、上記官能基の数と対応する。アーム部の数、すなわち上記官能基の数は、せん断安定性の観点から、２〜１２であることが好ましく、２〜８であることがより好ましく、３〜６であることが更に好ましい。 The number of arm portions of the poly (meth) acrylate viscosity index improver corresponds to the number of the functional groups. From the viewpoint of shear stability, the number of arm portions, that is, the number of functional groups is preferably 2 to 12, more preferably 2 to 8, and still more preferably 3 to 6.
本実施形態に係るポリ（メタ）アクリレート系粘度指数向上剤の製造方法としては、特に制限されないが、例えば、アルキル（メタ）アクリレート、開始剤及び溶媒を含む混合溶液に重合触媒を加え、アルキル（メタ）アクリレートを重合する方法が挙げられる。 Although it does not restrict | limit especially as a manufacturing method of the poly (meth) acrylate type viscosity index improver which concerns on this embodiment, For example, a polymerization catalyst is added to the mixed solution containing an alkyl (meth) acrylate, an initiator, and a solvent, and alkyl ( A method of polymerizing (meth) acrylate is mentioned.
アルキル（メタ）アクリレートとしては、下記一般式（３）で表されるアルキル（メタ）アクリレートを用いることができる。 As the alkyl (meth) acrylate, an alkyl (meth) acrylate represented by the following general formula (3) can be used.
式（３）中、Ｒ１は水素又はメチル基を示し、Ｒ２は炭素数１以上３６以下のアルキル基を示す。 In Formula (3), R 1 represents hydrogen or a methyl group, and R 2 represents an alkyl group having 1 to 36 carbon atoms.
Ｒ１はメチル基であることが好ましい。Ｒ２で示されるアルキル基の炭素数は、１〜３０であることが好ましく、１〜２６であることがより好ましく、１〜２２であることが更に好ましい。 R 1 is preferably a methyl group. The number of carbon atoms of the alkyl group represented by R 2 is preferably 1 to 30, more preferably 1 to 26, and still more preferably 1 to 22.
アルキル（メタ）アクリレートとしては、上記一般式（３）で表されるアルキル（メタ）アクリレートの１種を単独で、又は２種以上を混合して用いることができるが、２種以上を混合して用いることが好ましい。２種以上を混合して用いる場合、Ｒ２がメチル基であるメチル（メタ）アクリレートの含有量が、アルキル（メタ）アクリレート全量基準で、５〜５０質量％であることが好ましく、１０〜４５質量％であることがより好ましく、２０〜４５質量％であることが更に好ましい。また、Ｒ２が炭素数１８以上のアルキル基であるアルキル（メタ）アクリレートの含有量が、アルキル（メタ）アクリレート全量基準で、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましく、３０質量％以上であることが更に好ましい。 As the alkyl (meth) acrylate, one of the alkyl (meth) acrylates represented by the general formula (3) can be used alone, or two or more kinds can be used in combination. Are preferably used. When using 2 or more types mixedly, it is preferable that content of methyl (meth) acrylate whose R < 2 > is a methyl group is 5-50 mass% on the basis of alkyl (meth) acrylate whole quantity, More preferably, it is 20 mass%, and it is still more preferable that it is 20-45 mass%. It R 2 content of an alkyl (meth) acrylate an alkyl group having 18 or more carbon atoms is an alkyl (meth) acrylate total amount of preferably 10 mass% or more and 20 mass% or more Is more preferable, and it is still more preferable that it is 30 mass% or more.
開始剤としては、アクリロイル基の炭素−炭素二重結合と反応する官能基を３つ以上有する化合物に由来するものを用いることができ、例えば、１，１，１−トリス（２−ブロモイソブチルオキシメチレン）エタン、ペンタエリスリトールテトラキス（２−ブロモイソブチレート）、ジペンタエリスリトールヘキサキス（２−ブロモイソブチレート）を用いることができる。 As the initiator, one derived from a compound having three or more functional groups that react with the carbon-carbon double bond of the acryloyl group can be used. For example, 1,1,1-tris (2-bromoisobutyloxy Methylene) ethane, pentaerythritol tetrakis (2-bromoisobutyrate), dipentaerythritol hexakis (2-bromoisobutyrate) can be used.
溶媒としては、例えば、高度精製鉱油、アニソール、トルエンを用いることができる。好ましい溶媒としては、高度精製鉱油を例示することができる。 As the solvent, for example, highly refined mineral oil, anisole, and toluene can be used. As a preferred solvent, highly refined mineral oil can be exemplified.
重合触媒としては、例えば、臭化銅（ＩＩ）、トリス（２−ピリジルメチル）アミン、アゾビスイソブチロニトリル、２−エチルヘキサン酸スズ（ＩＩ）、トリス[２−（ジメチルアミノ）エチル]アミンを用いることができる。好ましい重合触媒としては、臭化銅（ＩＩ）、トリス（２−ピリジルメチル）アミン、アゾビスイソブチロニトリル、２−エチルヘキサン酸スズ（ＩＩ）を例示することができる。これらの重合触媒を１種単独で、又は２種以上を混合して用いてもよい。 Examples of the polymerization catalyst include copper (II) bromide, tris (2-pyridylmethyl) amine, azobisisobutyronitrile, tin (II) 2-ethylhexanoate, and tris [2- (dimethylamino) ethyl]. Amines can be used. Preferred examples of the polymerization catalyst include copper (II) bromide, tris (2-pyridylmethyl) amine, azobisisobutyronitrile, and tin (II) 2-ethylhexanoate. You may use these polymerization catalysts individually by 1 type or in mixture of 2 or more types.
アルキル（メタ）アクリレートを重合する際の反応温度は、適宜選定することができる。好ましい反応温度としては、６０〜１００℃を例示することができる。反応温度を上記範囲内にすることで、得られるポリ（メタ）アクリレート系粘度指数向上剤のＭｗ／Ｍｎが１．６以下となりやすくなる。例えば、反応温度が６０〜８０℃であるとＭｗ／Ｍｎが１．０〜１．３となる傾向にあり、反応温度が８０〜１００℃であるとＭｗ／Ｍｎが１．３〜１．６となる傾向にある。 The reaction temperature at the time of polymerizing the alkyl (meth) acrylate can be appropriately selected. As preferable reaction temperature, 60-100 degreeC can be illustrated. By setting the reaction temperature within the above range, the Mw / Mn of the resulting poly (meth) acrylate viscosity index improver tends to be 1.6 or less. For example, when the reaction temperature is 60 to 80 ° C., Mw / Mn tends to be 1.0 to 1.3, and when the reaction temperature is 80 to 100 ° C., Mw / Mn is 1.3 to 1.6. It tends to be.
反応時間は、原料であるアルキル（メタ）アクリレート、重合試薬、溶媒及び開始剤の種類及び使用量、反応温度等の反応条件、目的とするポリ（メタ）アクリレートのＭｗ及びＭｗ／Ｍｎに応じて適宜選定することができる。好ましい反応時間としては、８〜１６時間を例示することができる。 The reaction time depends on the reaction conditions such as the raw material alkyl (meth) acrylate, polymerization reagent, solvent and initiator, reaction temperature, and the like, and the desired poly (meth) acrylate Mw and Mw / Mn. It can be selected as appropriate. Examples of preferable reaction time include 8 to 16 hours.
アルキル（メタ）アクリレートの重合は、窒素雰囲気下で行うことが好ましい。 The polymerization of the alkyl (meth) acrylate is preferably performed in a nitrogen atmosphere.
［第２実施形態：潤滑油添加剤］
本発明の第２実施形態に係る潤滑油添加剤は、上記一般式（１）で表される構造単位を含む重合鎖を有し、重量平均分子量Ｍｗが１００，０００未満であり、重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎが１．６以下であるポリ（メタ）アクリレート系粘度指数向上剤を含有する。なお、本実施形態におけるポリ（メタ）アクリレート系粘度指数向上剤は、上記第１実施形態における粘度指数向上剤と同様であり、ここでは重複する説明を省略する。
[Second Embodiment: Lubricating Oil Additive]
The lubricating oil additive according to the second embodiment of the present invention has a polymer chain containing the structural unit represented by the general formula (1), has a weight average molecular weight Mw of less than 100,000, and a weight average molecular weight. A poly (meth) acrylate viscosity index improver having a ratio Mw / Mn of Mw to number average molecular weight Mn of 1.6 or less is contained. The poly (meth) acrylate-based viscosity index improver in the present embodiment is the same as the viscosity index improver in the first embodiment, and a duplicate description is omitted here.
潤滑油添加剤は、上記のポリ（メタ）アクリレート系粘度指数向上剤のみからなるものであってもよく、あるいは、当該粘度指数向上剤と他の添加剤との混合物（すなわち添加剤組成物）であってもよい。潤滑油添加剤が当該粘度指数向上剤と他の添加剤との混合物である場合、これらの混合割合は特に制限されず、用途に応じて適宜選定することができる。 The lubricating oil additive may consist only of the above poly (meth) acrylate viscosity index improver, or a mixture of the viscosity index improver and other additives (ie, additive composition). It may be. When the lubricating oil additive is a mixture of the viscosity index improver and other additives, the mixing ratio is not particularly limited and can be appropriately selected according to the application.
他の添加剤としては、上記のポリ（メタ）アクリレート系粘度指数向上剤以外の粘度指数向上剤、酸化防止剤、摩耗防止剤（又は極圧剤）、腐食防止剤、防錆剤、粘度指数向上剤、流動点降下剤、抗乳化剤、金属不活性化剤、消泡剤、無灰摩擦調整剤等の添加剤等が挙げられる。これらの添加剤は、１種を単独で、又は２種以上を組み合わせて用いることができる。 Other additives include viscosity index improvers other than the above poly (meth) acrylate viscosity index improvers, antioxidants, antiwear agents (or extreme pressure agents), corrosion inhibitors, rust inhibitors, viscosity indexes Examples thereof include additives such as improvers, pour point depressants, demulsifiers, metal deactivators, antifoaming agents, and ashless friction modifiers. These additives can be used individually by 1 type or in combination of 2 or more types.
上記のポリ（メタ）アクリレート系粘度指数向上剤以外の粘度指数向上剤としては、上記のポリ（メタ）アクリレート系粘度指数向上剤以外のポリ（メタ）アクリレート系粘度指数向上剤、ポリイソブテン系粘度指数向上剤、エチレン−プロピレン共重合体系粘度指数向上剤、スチレン−ブタジエン水添共重合体系粘度指数向上剤などが挙げられる。 As the viscosity index improver other than the above poly (meth) acrylate viscosity index improver, poly (meth) acrylate viscosity index improver other than the above poly (meth) acrylate viscosity index improver, polyisobutene viscosity index Examples thereof include an improver, an ethylene-propylene copolymer viscosity index improver, and a styrene-butadiene hydrogenated copolymer viscosity index improver.
酸化防止剤としては、フェノール系、アミン系等の無灰酸化防止剤、亜鉛系、銅系、モリブデン系等の金属系酸化防止剤が挙げられる。 Examples of the antioxidant include ashless antioxidants such as phenols and amines, and metal antioxidants such as zinc, copper, and molybdenum.
フェノール系酸化防止剤としては、例えば、４，４'−メチレンビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４’−ビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、４，４'−ビス（２−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２'−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、２，２'−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４'−ブチリデンビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−イソプロピリデンビス（２，６−ジ−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−ノニルフェノール）、２，２'−イソブチリデンビス（４，６−ジメチルフェノール）、２，２’−メチレンビス（４−メチル−６−シクロヘキシルフェノール）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−エチルフェノール、２，４−ジメチル−６−ｔｅｒｔ−ブチルフェノール、２，６−ジ−ｔｅｒｔ−α−ジメチルアミノ−ｐ−クレゾール、２，６−ジ−ｔｅｒｔ−ブチル−４−（Ｎ，Ｎ−ジメチルアミノメチルフェノール）、４,４'−チオビス（２−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４'−チオビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２'−チオビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、ビス（３−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルベンジル）スルフィド、ビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）スルフィド、２，２'−チオ−ジエチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、トリデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、ペンタエリスリチル−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクチル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、ステアリル３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、オクチル−３−（３−メチル−５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート等が挙げられる。これらは二種以上を混合して使用してもよい。 Examples of phenolic antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4 ′. -Bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6) -Nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl-6-silane) (Rohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6 -Di-tert-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethylphenol), 4,4'-thiobis (2-methyl-6- tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy) -5-tert-butylbenzyl) sulfide, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 2,2'-thio -Diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tridecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, stearyl 3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octyl-3- (3-methyl-5-di-tert-butyl-4-hydroxyphenyl) propionate, and the like. You may use these in mixture of 2 or more types.
アミン系酸化防止剤としては、例えば、芳香族アミン化合物、アルキルジフェニルアミン、アルキルナフチルアミン、フェニル−α−ナフチルアミン、アルキルフェニル−α−ナフチルアミン等の潤滑油用として一般に使用されている公知のアミン系酸化防止剤が挙げられる。 As the amine-based antioxidant, for example, known amine-based antioxidants generally used for lubricating oils such as aromatic amine compounds, alkyldiphenylamines, alkylnaphthylamines, phenyl-α-naphthylamines, alkylphenyl-α-naphthylamines, etc. Agents.
腐食防止剤としては、例えば、ベンゾトリアゾール系、トリルトリアゾール系、チアジアゾール系、又はイミダゾール系化合物等が挙げられる。 Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, or imidazole compounds.
防錆剤としては、例えば、石油スルホネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、アルケニルコハク酸エステル、又は多価アルコールエステル等が挙げられる。 Examples of the rust preventive include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
金属不活性化剤としては、例えば、イミダゾリン、ピリミジン誘導体、アルキルチアジアゾール、メルカプトベンゾチアゾール、ベンゾトリアゾール又はその誘導体、１，３，４−チアジアゾールポリスルフィド、１，３，４−チアジアゾリル−２，５−ビスジアルキルジチオカーバメート、２−（アルキルジチオ）ベンゾイミダゾール、又はβ−（ｏ−カルボキシベンジルチオ）プロピオンニトリル等が挙げられる。 Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.
消泡剤としては、例えば、２５℃における動粘度が１，０００〜１００，０００ｍｍ２／ｓのシリコーンオイル、アルケニルコハク酸誘導体、ポリヒドロキシ脂肪族アルコールと長鎖脂肪酸のエステル、メチルサリチレートとｏ−ヒドロキシベンジルアルコール等が挙げられる。 Examples of antifoaming agents include silicone oils having a kinematic viscosity at 25 ° C. of 1,000 to 100,000 mm 2 / s, alkenyl succinic acid derivatives, esters of polyhydroxy aliphatic alcohols and long chain fatty acids, and methyl salicylates. o-Hydroxybenzyl alcohol and the like can be mentioned.
無灰摩擦調整剤としては、潤滑油用の無灰摩擦調整剤として通常用いられる任意の化合物が使用可能であり、例えば、炭素数６〜３０のアルキル基又はアルケニル基、特に炭素数６〜３０の直鎖アルキル基又は直鎖アルケニル基を分子中に少なくとも１個有する、アミン化合物、脂肪酸エステル、脂肪酸アミド、脂肪酸、脂肪族アルコール、脂肪族エーテル等の無灰摩擦調整剤等が挙げられる。また特開２００９−２８６８３１号公報に記載の窒素含有化合物及びその酸変性誘導体等、国際公開第２００５／０３７９６７号パンフレットに例示されている各種無灰摩擦調整剤を用いることもできる。 As the ashless friction modifier, any compound usually used as an ashless friction modifier for lubricating oils can be used, for example, an alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly 6 to 30 carbon atoms. And ashless friction modifiers such as amine compounds, fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols and aliphatic ethers having at least one linear alkyl group or linear alkenyl group in the molecule. Various ashless friction modifiers exemplified in International Publication No. 2005/037967 pamphlet such as nitrogen-containing compounds and acid-modified derivatives thereof described in JP-A-2009-286831 can also be used.
また、本実施形態に係る潤滑油添加剤は、溶剤を更に含有していてもよい。溶剤としては、高度精製鉱油、溶剤精製基油、合成油を用いることができる。これらの中でも、高度精製鉱油を用いることが好ましい。潤滑油添加剤が溶剤を含有する場合、溶剤の含有量は、潤滑油添加剤の全量を基準として、好ましくは５〜７５質量％、より好ましくは３０〜６０質量％である。 Moreover, the lubricating oil additive according to this embodiment may further contain a solvent. As the solvent, highly refined mineral oil, solvent refined base oil, and synthetic oil can be used. Among these, it is preferable to use highly refined mineral oil. When the lubricating oil additive contains a solvent, the content of the solvent is preferably 5 to 75 mass%, more preferably 30 to 60 mass%, based on the total amount of the lubricating oil additive.
［第３実施形態：潤滑油組成物］
第３実施形態に係る潤滑油組成物は、潤滑油基油と、上記一般式（１）で表される構造単位を含む重合鎖を有し、重量平均分子量Ｍｗが１００，０００未満であり、重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎが１．６以下であるポリ（メタ）アクリレート系粘度指数向上剤と、を含有する。ここで、本実施形態に係る潤滑油組成物には、潤滑油基油と上記第２の実施形態に係る潤滑油添加剤とを含有する態様が包含される。本実施形態におけるポリ（メタ）アクリレート系粘度指数向上剤は上記第１実施形態及び第２実施形態におけるポリ（メタ）アクリレート系粘度指数向上剤と同様であり、また、潤滑油組成物に含まれ得るその他の添加剤及び溶剤は第２実施形態におけるその他の添加剤及び溶剤と同様であり、ここでは重複する説明を省略する。
[Third Embodiment: Lubricating Oil Composition]
The lubricating oil composition according to the third embodiment has a lubricating base oil and a polymer chain containing the structural unit represented by the general formula (1), and the weight average molecular weight Mw is less than 100,000, And a poly (meth) acrylate viscosity index improver having a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 1.6 or less. Here, the lubricating oil composition according to the present embodiment includes a mode including the lubricating base oil and the lubricating oil additive according to the second embodiment. The poly (meth) acrylate-based viscosity index improver in the present embodiment is the same as the poly (meth) acrylate-based viscosity index improver in the first embodiment and the second embodiment, and is included in the lubricating oil composition. The other additives and solvents to be obtained are the same as the other additives and solvents in the second embodiment, and redundant description is omitted here.
潤滑油基油としては、特に制限されず、通常の潤滑油に使用される潤滑油基油を使用できる。具体的には、鉱油系潤滑油基油、合成油系潤滑油基油又はこれらの中から選ばれる２種以上の潤滑油基油を任意の割合で混合した混合物等を使用できる。 The lubricating base oil is not particularly limited, and a lubricating base oil used for ordinary lubricating oil can be used. Specifically, a mineral oil base oil, a synthetic oil base oil, or a mixture of two or more kinds of lubricant base oils selected from these can be used.
鉱油系潤滑油基油としては、例えば、原油を常圧蒸留して得られる常圧残油を減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、水素化精製等の処理を１つ以上行って精製したもの、あるいはワックス異性化鉱油、ＧＴＬワックス（ガストゥリキッドワックス）を異性化する手法で製造される基油等が挙げられる。 Examples of mineral oil base oils include, for example, solvent oil removal, solvent extraction, hydrocracking, solvent removal of lubricating oil fractions obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil. Examples thereof include those refined by performing one or more treatments such as dewaxing and hydrorefining, or base oils produced by a method of isomerizing wax isomerized mineral oil or GTL wax (gas-tuly wax).
合成油系潤滑油としては、例えば、ポリブテン又はその水素化物；１−オクテンオリゴマー、１−デセンオリゴマー等のポリ−α−オレフィン又はその水素化物；ジトリデシルグルタレート、ジ−２−エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、ジ−２−エチルヘキシルセバケート等のジエステル；トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール−２−エチルヘキサノエート、ペンタエリスリトールペラルゴネート等のポリオールエステル；アルキルナフタレン、アルキルベンゼン等の芳香族系合成油又はこれらの混合物等が例示できる。 Synthetic oil-based lubricating oils include, for example, polybutene or hydrides thereof; poly-α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl Diesters such as adipate, ditridecyl adipate, di-2-ethylhexyl sebacate; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate; alkylnaphthalene And aromatic synthetic oils such as alkylbenzene or mixtures thereof.
潤滑油基油の１００℃における動粘度は、好ましくは２．５〜１０．０ｍｍ２／ｓ、より好ましくは３．０〜８．０ｍｍ２／ｓ、更に好ましくは３．５〜６．０ｍｍ２／ｓである。また、潤滑油基油の粘度指数は、好ましくは９０〜１６５、より好ましくは１００〜１５５、更に好ましくは１２０〜１５０である。 The kinematic viscosity of the lubricating base oil at 100 ° C. is preferably 2.5 to 10.0 mm 2 / s, more preferably 3.0 to 8.0 mm 2 / s, still more preferably 3.5 to 6.0 mm 2. / S. The viscosity index of the lubricating base oil is preferably 90 to 165, more preferably 100 to 155, and still more preferably 120 to 150.
潤滑油基油のクロマト分析による飽和分は、第１実施形態に係るポリ（メタ）アクリレート系粘度指数向上剤等の添加剤の効果を発揮しやすくするため、好ましくは８０％以上、より好ましくは８５％以上、更に好ましくは９０％以上、最も好ましくは９５％以上である。 The saturated content of the lubricating base oil by chromatographic analysis is preferably 80% or more, more preferably, in order to facilitate the effects of additives such as the poly (meth) acrylate viscosity index improver according to the first embodiment. 85% or more, more preferably 90% or more, and most preferably 95% or more.
第１実施形態に係るポリ（メタ）アクリレート系粘度指数向上剤の含有量は、潤滑油組成物全量を基準として、好ましくは０．１〜２０．０質量％、より好ましくは０．５〜１５．０質量％、更に好ましくは１．０〜１０．０質量％である。当該含有量が上記下限値以上であると、十分な添加効果を得られやすくなり、一方、当該含有量が上記上限値以下であると、せん断安定性が高くなり、燃費持続性が向上する。 The content of the poly (meth) acrylate viscosity index improver according to the first embodiment is preferably 0.1 to 20.0 mass%, more preferably 0.5 to 15 based on the total amount of the lubricating oil composition. It is 0.0 mass%, More preferably, it is 1.0-10.0 mass%. When the content is equal to or higher than the lower limit value, it is easy to obtain a sufficient addition effect. On the other hand, when the content is equal to or lower than the upper limit value, shear stability is increased and fuel consumption sustainability is improved.
潤滑油組成物の１００℃における動粘度は、好ましくは２．０〜１６．３ｍｍ２／ｓ、より好ましくは２．５〜１２．５ｍｍ２／ｓ、更に好ましくは３．０〜１０．０ｍｍ２／ｓである。１００℃における動粘度が上記下限値以上であると、潤滑性を確保しやすくなり、一方、１００℃における動粘度が上記上限値以下であると、より省燃費性が向上する。なお、本発明での１００℃における動粘度は、ＪＩＳ Ｋ−２２８３−１９９３に規定される１００℃における動粘度を意味する。 The kinematic viscosity at 100 ° C. of the lubricating oil composition is preferably 2.0 to 16.3 mm 2 / s, more preferably 2.5 to 12.5 mm 2 / s, still more preferably 3.0 to 10.0 mm 2. / S. When the kinematic viscosity at 100 ° C. is not less than the above lower limit value, it becomes easy to ensure lubricity, while when the kinematic viscosity at 100 ° C. is not more than the above upper limit value, fuel economy is further improved. The kinematic viscosity at 100 ° C. in the present invention means the kinematic viscosity at 100 ° C. defined in JIS K-2283-1993.
潤滑油組成物の粘度指数は、好ましくは１３０〜２５０、より好ましくは１４０〜２４０、更に好ましくは１６０〜２３０である。粘度指数が上記下限値以上であると、ＨＴＨＳ粘度を維持しながら、より省燃費性を向上させることができ、また低温粘度を低下させやすくなる。一方、粘度指数が上記上限値以下であると、低温流動性、添加剤の溶解性、及びシール材料との適合性を確保することができる。なお、本発明での粘度指数は、ＪＩＳ Ｋ ２２８３−１９９３に規定される粘度指数を意味する。 The viscosity index of the lubricating oil composition is preferably 130 to 250, more preferably 140 to 240, and still more preferably 160 to 230. When the viscosity index is equal to or higher than the lower limit, fuel economy can be further improved while maintaining the HTHS viscosity, and the low temperature viscosity is easily lowered. On the other hand, when the viscosity index is less than or equal to the above upper limit, low temperature fluidity, solubility of additives, and compatibility with sealing materials can be ensured. In addition, the viscosity index in this invention means the viscosity index prescribed | regulated to JISK2283-1993.
潤滑油組成物のせん断率は、好ましくは８％以下、より好ましくは５％以下、更に好ましくは２％以下である。せん断率が上記上限値以下であると、処方油をさらに低粘度化することが可能である。なお、本発明でのせん断率は、実機のギヤでのせん断安定性をシミュレートするためにＫＲＬテーパーローラーベアリング（試験法：ＣＥＣ Ｌ４５−Ａ−９９）を用い、機械的せん断による方法で評価したせん断率を意味する。より詳細には、ＧｒｏｕｐＩＩの基油に粘度指数向上剤を２質量％になるように調製したものを、上記試験法に準拠し、１２０時間連続で運転する。そのときの、試験前後での１００℃の動粘度の低下率（試験前後での動粘度との差を試験前の動粘度で割った値（％））をせん断率とする。 The shear rate of the lubricating oil composition is preferably 8% or less, more preferably 5% or less, and still more preferably 2% or less. When the shear rate is less than or equal to the above upper limit, the viscosity of the formulated oil can be further reduced. The shear rate in the present invention was evaluated by a mechanical shearing method using a KRL taper roller bearing (test method: CEC L45-A-99) in order to simulate shear stability in a real gear. Means shear rate. More specifically, a Group II base oil prepared with a viscosity index improver of 2% by mass is operated continuously for 120 hours in accordance with the above test method. The shear rate is the rate of decrease in kinematic viscosity at 100 ° C. before and after the test (the value (%) obtained by dividing the difference from the kinematic viscosity before and after the test by the kinematic viscosity before the test).
以上説明した第１実施形態に係る粘度指数向上剤、第２実施形態に係る潤滑油添加剤、及び第３実施形態に係る潤滑油組成物は、内燃機関用潤滑油、駆動系潤滑油等の幅広い分野で使用することができるが、特に、駆動系潤滑油の分野において有用である。この場合の駆動装置は自動変速機（ＡＴ）、無段自動変速機（ＣＶＴ）および有段変速機（ＴＭ）のいずれであってもよい。 The viscosity index improver according to the first embodiment described above, the lubricating oil additive according to the second embodiment, and the lubricating oil composition according to the third embodiment include a lubricating oil for an internal combustion engine, a drive system lubricating oil, and the like. Although it can be used in a wide range of fields, it is particularly useful in the field of drive system lubricants. The driving device in this case may be any of an automatic transmission (AT), a continuously variable automatic transmission (CVT), and a stepped transmission (TM).
以下、実施例を挙げて本発明をより具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to a following example at all.
［実施例１］
下記の条件（「合成条件１」とする）でポリ（メタ）アクリレート系粘度指数向上剤を合成した。
[Example 1]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 1”).
錨型金属製攪拌翼（真空シール付）、ジムロート冷却器、窒素導入用３方コック及びサンプル導入口を装着した３００ｍｌの５口セパラブルフラスコに、メチルメタクリレート（式（３）中のＲ１及びＲ２が共にメチル基である化合物。以下「Ｃ１−ＭＡ」と表記する。）１８ｇ、ステアリルメタクリレート（式（３）中のＲ１がメチル基、Ｒ２がステアリル基（炭素数１８の直鎖アルキル基）である化合物。以下「Ｃ１８−ＭＡ」と表記する。）４２ｇ、開始剤として３官能開始剤である１，１，１−トリス（２−ブロモイソブチロキシメチル）エタン（以下「Ｘ」と表記する。）０．１８ｇ、及び溶媒として高度精製鉱油（１００℃の動粘度：４．２ｍｍ２／ｓ）１１７ｇを投入し、攪拌下で均一溶液とした。本溶液を氷浴にて０℃まで冷却し、ダイヤフラムポンプを用いて反応系の真空脱気／窒素パージを５回実施した。さらに、窒素フロー下でサンプル導入口より、重合触媒として臭化銅（ＩＩ）０．００４ｇ及びトリス（２−ピリジルメチル）アミン０．００５ｇをアニソール２．０ｇに溶解した錯体溶液と、アゾビスイソブチロニトリル（ＡＩＢＮ）０．０５６ｇとを投入した後、窒素雰囲気下にて溶液温度７０℃にて１２時間撹拌して重合を実施し、３つのアーム部を有するポリ（メタ）アクリレート系粘度指数向上剤を含有した溶液を得た。 A 300 ml five-neck separable flask equipped with a vertical metal stirring blade (with vacuum seal), a Dimroth cooler, a three-way cock for introducing nitrogen and a sample inlet was charged with methyl methacrylate (R 1 in formula (3) and Compound in which R 2 is both a methyl group, hereinafter referred to as “C1-MA”) 18 g, stearyl methacrylate (in formula (3), R 1 is a methyl group, R 2 is a stearyl group (straight chain of 18 carbon atoms) 42g, trifunctional initiator 1,1,1-tris (2-bromoisobutyroxymethyl) ethane (hereinafter referred to as “X”). And 0.18 g of highly refined mineral oil (kinematic viscosity at 100 ° C .: 4.2 mm 2 / s) as a solvent was added, and a uniform solution was obtained under stirring. This solution was cooled to 0 ° C. in an ice bath, and vacuum degassing / nitrogen purging of the reaction system was performed 5 times using a diaphragm pump. Further, from a sample inlet under a nitrogen flow, a complex solution in which 0.004 g of copper (II) bromide and 0.005 g of tris (2-pyridylmethyl) amine as a polymerization catalyst were dissolved in 2.0 g of anisole, and azobisiso After adding 0.056 g of butyronitrile (AIBN), polymerization was carried out by stirring for 12 hours at a solution temperature of 70 ° C. in a nitrogen atmosphere, and a poly (meth) acrylate viscosity index having three arm parts A solution containing an improver was obtained.
得られたポリ（メタ）アクリレート系粘度指数向上剤について、ＧＰＣ分析により、重量平均分子量Ｍｗ及び数平均分子量Ｍｎを測定した。その結果、重量平均分子量Ｍｗは９７，０００、数平均分子量Ｍｎは６４，０００、Ｍｗ／Ｍｎは１．５１であった。ＧＰＣ分析の手順は以下のとおりである。 About the obtained poly (meth) acrylate type viscosity index improver, the weight average molecular weight Mw and the number average molecular weight Mn were measured by GPC analysis. As a result, the weight average molecular weight Mw was 97,000, the number average molecular weight Mn was 64,000, and Mw / Mn was 1.51. The procedure of GPC analysis is as follows.
溶剤としてテトラヒドロフランを使用し、希釈して試料濃度を２質量％とした溶液を調製した。その試料溶液を、ＧＰＣ装置（Ｗａｔｅｒｓ Ａｌｌｉａｎｃｅ２６９５）を用いて分析を行った。溶剤の流速は１ｍｌ／ｍｉｎ、分析可能分子量１０，０００から２５６，０００のカラムを使用し、屈折率を検出器として分析を実施した。なお、分子量が明確なポリスチレン標準を用いてカラム保持時間と分子量との関係を求め、検量線を別途作成した上で、得られた保持時間から分子量を決定した。 Tetrahydrofuran was used as a solvent and diluted to prepare a solution having a sample concentration of 2% by mass. The sample solution was analyzed using a GPC apparatus (Waters Alliance 2695). The analysis was carried out using a column with a solvent flow rate of 1 ml / min and an analyzable molecular weight of 10,000 to 256,000 and using the refractive index as a detector. The relationship between the column retention time and the molecular weight was determined using a polystyrene standard with a clear molecular weight, a calibration curve was prepared separately, and the molecular weight was determined from the obtained retention time.
［実施例７］
下記の条件（「合成条件２」とする）でポリ（メタ）アクリレート系粘度指数向上剤を合成した。
[Example 7]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 2”).
錨型金属製攪拌翼（真空シール付）、ジムロート冷却器、窒素導入用３方コック及びサンプル導入口を装着した３００ｍｌの５口セパラブルフラスコに、メチルメタクリレート（Ｃ１−ＭＡ）１８ｇ、ステアリルメタクリレート（Ｃ１８−ＭＡ）４２ｇ、開始剤として３官能開始剤である１，１，１−トリス（２−ブロモイソブチロキシメチル）エタン（Ｘ）０．１４ｇ、及び溶媒として高度精製鉱油（１００℃の動粘度：４．２ｍｍ２／ｓ）１１７ｇを投入し、攪拌下で均一溶液とした。本溶液を氷浴にて０℃まで冷却し、ダイヤフラムポンプを用いて反応系の真空脱気／窒素パージを５回実施した。さらに、窒素フロー下でサンプル導入口より、重合触媒として臭化銅（ＩＩ）０．００４ｇ及びトリス（２−ピリジルメチル）アミン０．００５ｇをアニソール２．０ｇに溶解した錯体溶液と、２−エチルヘキサン酸スズ（ＩＩ）０．１７ｇを高度精製鉱油（１００℃の動粘度：４．２ｍｍ２／ｓ）３ｇに溶解した溶液とを投入した後、窒素雰囲気下にて溶液温度７０℃にて１２時間撹拌して重合を実施し、３つのアーム部を有するポリ（メタ）アクリレート系粘度指数向上剤を含有した溶液を得た。 A 300 ml 5-neck separable flask equipped with a vertical metal stirring blade (with vacuum seal), a Dimroth cooler, a 3-way cock for introducing nitrogen and a sample inlet, 18 g of methyl methacrylate (C1-MA), stearyl methacrylate ( C18-MA) 42 g, trifunctional initiator 1,1,1-tris (2-bromoisobutyroxymethyl) ethane (X) 0.14 g as initiator, and highly refined mineral oil (100 ° C. (Viscosity: 4.2 mm 2 / s) 117 g was added, and a uniform solution was obtained under stirring. This solution was cooled to 0 ° C. in an ice bath, and vacuum degassing / nitrogen purging of the reaction system was performed 5 times using a diaphragm pump. Furthermore, a complex solution prepared by dissolving 0.004 g of copper (II) bromide and 0.005 g of tris (2-pyridylmethyl) amine as a polymerization catalyst in 2.0 g of anisole from a sample introduction port under a nitrogen flow, and 2-ethyl A solution in which 0.17 g of tin (II) hexanoate was dissolved in 3 g of highly refined mineral oil (kinematic viscosity at 100 ° C .: 4.2 mm 2 / s) was added, and the solution was then added at a solution temperature of 70 ° C. under a nitrogen atmosphere. Polymerization was carried out by stirring for a time to obtain a solution containing a poly (meth) acrylate viscosity index improver having three arm portions.
得られたポリ（メタ）アクリレート系粘度指数向上剤について、実施例１と同様にＧＰＣ分析を行った結果、重量平均分子量Ｍｗは９８，０００、数平均分子量Ｍｎは８０，３００、Ｍｗ／Ｍｎは１．２２であった。 The obtained poly (meth) acrylate viscosity index improver was subjected to GPC analysis in the same manner as in Example 1. As a result, the weight average molecular weight Mw was 98,000, the number average molecular weight Mn was 80,300, and Mw / Mn was 1.22.
［比較例３］
下記の条件（「合成条件３」とする）でポリ（メタ）アクリレート系粘度指数向上剤を合成した。
[Comparative Example 3]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 3”).
錨型金属製攪拌翼（真空シール付）、ジムロート冷却器、窒素導入用３方コック及びサンプル導入口を装着した３００ｍｌの５口セパラブルフラスコに、メチルメタクリレート（Ｃ１−ＭＡ）１８ｇ、ステアリルメタクリレート（Ｃ１８−ＭＡ）４２ｇ、クミルジチオ安息香酸（ＣＤＴＢＡ）０．６５ｇ、及び溶媒として高度精製鉱油（１００℃の動粘度：４．２ｍｍ２／ｓ）６０ｇを投入し、攪拌下で均一溶液とした。本溶液を氷浴にて０℃まで冷却し、ダイヤフラムポンプを用いて反応系の真空脱気／窒素パージを５回実施した。さらに、窒素フロー下でサンプル導入口より開始剤としてアゾビスイソブチロニトリル（ＡＩＢＮ）０．０６ｇを投入した後、窒素雰囲気下にて溶液温度９０℃で１２時間重合を実施し、ポリ（メタ）アクリレート系粘度指数向上剤を含有した溶液を得た。 A 300 ml five-neck separable flask equipped with a vertical metal stirring blade (with vacuum seal), a Dimroth cooler, a three-way cock for introducing nitrogen and a sample inlet, 18 g of methyl methacrylate (C1-MA), stearyl methacrylate ( C18-MA) (42 g), cumyldithiobenzoic acid (CDTBA) (0.65 g), and highly purified mineral oil (kinematic viscosity at 100 ° C .: 4.2 mm 2 / s) as a solvent (60 g) were added to obtain a homogeneous solution under stirring. This solution was cooled to 0 ° C. in an ice bath, and vacuum degassing / nitrogen purging of the reaction system was performed 5 times using a diaphragm pump. Furthermore, 0.06 g of azobisisobutyronitrile (AIBN) was added as an initiator from the sample inlet under a nitrogen flow, and then polymerization was performed at a solution temperature of 90 ° C. for 12 hours in a nitrogen atmosphere. ) A solution containing an acrylate viscosity index improver was obtained.
得られたポリ（メタ）アクリレート系粘度指数向上剤について、実施例１と同様にＧＰＣ分析を行った結果、重量平均分子量Ｍｗは９０，０００、数平均分子量Ｍｎは５４，０００、Ｍｗ／Ｍｎは１．７１であった。 The obtained poly (meth) acrylate viscosity index improver was subjected to GPC analysis in the same manner as in Example 1. As a result, the weight average molecular weight Mw was 90,000, the number average molecular weight Mn was 54,000, and Mw / Mn was 1.71.
［比較例５］
下記の条件（「合成条件４」とする）でポリ（メタ）アクリレート系粘度指数向上剤を合成した。
[Comparative Example 5]
A poly (meth) acrylate viscosity index improver was synthesized under the following conditions (referred to as “synthesis condition 4”).
撹拌羽（真空シール付）、ジムロート冷却器、窒素導入用３方コック及びサンプル導入用滴下ロートを装着した３００ｍｌの４口の反応フラスコに、溶媒として高度精製鉱油３０ｇを投入し、８５℃の油浴内で窒素パージを実施しながら１時間撹拌した。サンプル導入用滴下ロートに、原料モノマーとしてメチルメタクリレート（Ｃ１−ＭＡ）１２ｇ及びステアリルメタクリレート（Ｃ１８−ＭＡ）４２ｇ、開始剤としてアゾビスイソブチロニトリル（ＡＩＢＮ）０．２４ｇを混合した原料を投入し、この原料を１２０分かけて反応フラスコ内に滴下した。その後、窒素フロー下にて８５℃で撹拌を保持して８時間重合を実施し、ポリ（メタ）アクリレート系粘度指数向上剤を含有した溶液を得た。その後、１３０℃、１ｍｍＨｇで３時間真空蒸留を実施して、上記溶液から未反応モノマーを除去した。 A 300 ml four-necked reaction flask equipped with a stirring blade (with vacuum seal), a Dimroth cooler, a three-way cock for introducing nitrogen, and a dropping funnel for introducing sample was charged with 30 g of highly purified mineral oil as a solvent, and an oil at 85 ° C. The mixture was stirred for 1 hour while purging with nitrogen in the bath. A raw material in which 12 g of methyl methacrylate (C1-MA) and 42 g of stearyl methacrylate (C18-MA) are mixed as raw material monomers and 0.24 g of azobisisobutyronitrile (AIBN) as an initiator is charged into a dropping funnel for sample introduction. This raw material was dropped into the reaction flask over 120 minutes. Thereafter, polymerization was carried out for 8 hours while maintaining stirring at 85 ° C. under a nitrogen flow to obtain a solution containing a poly (meth) acrylate viscosity index improver. Thereafter, vacuum distillation was performed at 130 ° C. and 1 mmHg for 3 hours to remove unreacted monomers from the solution.
得られたポリ（メタ）アクリレート系粘度指数向上剤について、実施例１と同様にＧＰＣ分析を行った結果、重量平均分子量Ｍｗは９７，０００、数平均分子量Ｍｎは４２，５００、Ｍｗ／Ｍｎは２．２８であった。 The obtained poly (meth) acrylate viscosity index improver was subjected to GPC analysis in the same manner as in Example 1. As a result, the weight average molecular weight Mw was 97,000, the number average molecular weight Mn was 42,500, and Mw / Mn was 2.28.
［実施例２〜６、８〜２８、比較例１〜２、４、６］
原料の配合量を表１、３、５、７、９、１１に示すとおりに変更し、それ以外は上記の合成条件１〜４のいずれかと同様にして、ポリ（メタ）アクリレート系粘度指数向上剤を合成した。なお、表中、Ｙは４官能開始剤であるペンタエリスリトールテトラキス（２−ブロモイソブチレート）、Ｚは６官能開始剤であるジペンタエリスリトールヘキサキス（２−ブロモイソブチレート）を表す。また、２ＥＨ−ＭＡは、式（１）中のＲ１がメチル基、Ｒ２が２−エチルヘキシル基（炭素数２の分岐を１つ有する、合計の炭素数８のアルキル基）である化合物、Ｃ１２−ＭＡは、式（３）中のＲ１がメチル基、Ｒ２がドデシル基（炭素数１２の直鎖アルキル基）である化合物それぞれを表す。得られたポリ（メタ）アクリレート系粘度指数向上剤のＭｗ、Ｍｎ及びＭｗ／Ｍｎを表２、４、６、８、１０、１２に示す。
[Examples 2-6, 8-28, Comparative Examples 1-2, 4, 6]
The blending amount of the raw materials is changed as shown in Tables 1, 3, 5, 7, 9, and 11, and the other conditions are the same as those in any one of the above synthesis conditions 1 to 4, and the poly (meth) acrylate viscosity index is improved. The agent was synthesized. In the table, Y represents pentaerythritol tetrakis (2-bromoisobutyrate) which is a tetrafunctional initiator, and Z represents dipentaerythritol hexakis (2-bromoisobutyrate) which is a hexafunctional initiator. 2EH-MA is a compound in which R 1 in formula (1) is a methyl group, and R 2 is a 2-ethylhexyl group (a total of 8 alkyl groups having one branch having 2 carbon atoms), C12-MA represents each compound in which R 1 in formula (3) is a methyl group and R 2 is a dodecyl group (a linear alkyl group having 12 carbon atoms). Tables 2, 4, 6, 8, 10, and 12 show Mw, Mn, and Mw / Mn of the obtained poly (meth) acrylate viscosity index improvers.
＜潤滑油組成物の調製＞
実施例１〜２８及び比較例１〜６でそれぞれ得られたポリ（メタ）アクリレート系粘度指数向上剤と、金属系（ＴＢＮ３００ｍｇＫＯＨ/ｇのカルシウムスルホネート系）清浄剤、無灰分残剤（コハク酸イミド）、摩擦調整剤（オレイルアミド）、摩耗防止剤（リン酸）、酸化防止剤（ジフェニルアミン）、金属不活性化剤（チアジアゾール）、及び硫黄系添加剤（硫化エステル）を含む性能添加剤と、高度精製鉱油（ＧｒｏｕｐＩＩ基油、１００℃における動粘度：３．３ｍｍ２／ｓ、ＶＩ：１１０）とを、表２、４、６、８、１０、１２に示す割合で配合し、潤滑油組成物を調製した。
<Preparation of lubricating oil composition>
Poly (meth) acrylate viscosity index improvers obtained in Examples 1 to 28 and Comparative Examples 1 to 6, metal (TBN 300 mg KOH / g calcium sulfonate) detergents, ashless residue (succinimide) ), A friction modifier (oleylamide), an antiwear agent (phosphoric acid), an antioxidant (diphenylamine), a metal deactivator (thiadiazole), and a sulfur-based additive (sulfurized ester), and a performance additive, Highly refined mineral oil (Group II base oil, kinematic viscosity at 100 ° C .: 3.3 mm 2 / s, VI: 110) is blended in the ratios shown in Tables 2, 4, 6, 8, 10, 12 and lubricating oil composition A product was prepared.
＜潤滑油組成物の評価＞
実施例１〜２８及び比較例１〜６の各潤滑油組成物について、１００℃における動粘度、粘度指数、及びせん断安定性を、それぞれ下記に準拠した方法により測定した。結果を表２、４、６、８、１０に示す。
動粘度：ＪＩＳ Ｋ−２２８３−１９９３
粘度指数：ＪＩＳ Ｋ ２２８３−１９９３
<Evaluation of lubricating oil composition>
About each lubricating oil composition of Examples 1-28 and Comparative Examples 1-6, the kinematic viscosity in 100 degreeC, the viscosity index, and the shear stability were measured by the method based on the following, respectively. The results are shown in Tables 2, 4, 6, 8, and 10.
Kinematic viscosity: JIS K-2283-1993
Viscosity index: JIS K 2283-1993
また、実施例１〜２８及び比較例１〜６の各潤滑油組成物の摩擦特性を、二円筒転がりすべり摩擦試験機を用いて、一定荷重条件下での摩擦係数により評価した。具体的には、試験温度８０℃、荷重１４２Ｎ、面圧０．４８ＧＰａ、周速１．０ｍ／ｓ、すべり率５.１％の条件で、試験開始から１０分間の摩擦係数を平均化した。結果を表２、４、６、８、１０、１２に示す。 In addition, the friction characteristics of each of the lubricating oil compositions of Examples 1 to 28 and Comparative Examples 1 to 6 were evaluated by a friction coefficient under a constant load condition using a two-cylinder rolling sliding friction tester. Specifically, the friction coefficient for 10 minutes from the start of the test was averaged under the conditions of a test temperature of 80 ° C., a load of 142 N, a surface pressure of 0.48 GPa, a peripheral speed of 1.0 m / s, and a slip ratio of 5.1%. The results are shown in Tables 2, 4, 6, 8, 10, and 12.
また、実施例１〜２８及び比較例１〜６の各粘度指数向上剤を用いたときのせん断安定性を、実機のギヤでのせん断安定性をシミュレートするためにＫＲＬテーパーローラーベアリング（試験法：ＣＥＣ Ｌ４５−Ａ−９９）を用い、機械的せん断による方法で評価した。より詳細には、ＧｒｏｕｐＩＩの基油に各粘度指数向上剤を２質量％になるように調製したものを、上記試験法に準拠し、１２０時間連続で運転した。そのときの、試験前後での１００℃の動粘度の低下率（試験前後での動粘度との差を試験前の動粘度で割った値（％））をせん断率として評価した。 Moreover, in order to simulate the shear stability when using the viscosity index improvers of Examples 1 to 28 and Comparative Examples 1 to 6, the KRL taper roller bearing (test method) : CEC L45-A-99), and evaluated by a mechanical shearing method. More specifically, a Group II base oil prepared with 2% by mass of each viscosity index improver was operated continuously for 120 hours in accordance with the above test method. The rate of decrease in kinematic viscosity at 100 ° C. before and after the test (value (%) obtained by dividing the difference from the kinematic viscosity before and after the test by the kinematic viscosity before the test) was evaluated as the shear rate.
Claims (3)
重量平均分子量Ｍｗが１００，０００未満であり、重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎが１．６以下である、ポリ（メタ）アクリレート系粘度指数向上剤。
［式（１）中、Ｒ１は水素又はメチル基を示し、Ｒ２は炭素数１以上３６以下のアルキル基を示す。］ A polymer chain comprising a core and a structural unit represented by the following general formula (1), wherein the structural unit in which R 2 in the general formula (1) is a methyl group is contained in the polymer chain total amount 15 to 45 wt% viewed contains a reference, and, R 2 is a polymer chain containing more than 10 wt% based on the total amount of the structural unit contained a structural unit is an alkyl group having 18 or more carbon atoms in the polymer chain And three or more arm portions, one end of the polymer chain being bonded to the core portion,
A poly (meth) acrylate viscosity index improver having a weight average molecular weight Mw of less than 100,000 and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 1.6 or less.
[In Formula (1), R 1 represents hydrogen or a methyl group, and R 2 represents an alkyl group having 1 to 36 carbon atoms. ]
A lubricating oil composition comprising a lubricating base oil and the poly (meth) acrylate viscosity index improver according to claim 1.
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| US14/413,573 US9783757B2 (en) | 2012-07-24 | 2013-07-24 | Poly(meth)acrylate-based viscosity index improver, lubricant additive and lubricant composition containing viscosity index improver |
| CN201380033976.2A CN104395444B (en) | 2012-07-24 | 2013-07-24 | Poly- (methyl) acrylic ester viscosity index improver and the lube oil additive containing the viscosity index improver and lubricant oil composite |
| EP13822773.1A EP2878656B1 (en) | 2012-07-24 | 2013-07-24 | Poly(meth)acrylate-based viscosity index improver, lubricant additive and lubricant composition containing viscosity index improver |
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