CN1333057C - Lubricating oil composition and internal combustion engine oil - Google Patents
Lubricating oil composition and internal combustion engine oil Download PDFInfo
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- CN1333057C CN1333057C CNB2003801029420A CN200380102942A CN1333057C CN 1333057 C CN1333057 C CN 1333057C CN B2003801029420 A CNB2003801029420 A CN B2003801029420A CN 200380102942 A CN200380102942 A CN 200380102942A CN 1333057 C CN1333057 C CN 1333057C
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- propylene copolymer
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000010705 motor oil Substances 0.000 title abstract description 7
- 238000002485 combustion reaction Methods 0.000 title abstract 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 79
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003921 oil Substances 0.000 claims abstract description 22
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 74
- 239000002480 mineral oil Substances 0.000 claims description 27
- 235000010446 mineral oil Nutrition 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 10
- 238000000646 scanning calorimetry Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012208 gear oil Substances 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 abstract description 2
- 230000000994 depressogenic effect Effects 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 40
- 238000000034 method Methods 0.000 description 25
- 239000000126 substance Substances 0.000 description 22
- 230000008569 process Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003599 detergent Substances 0.000 description 15
- 239000002270 dispersing agent Substances 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000002199 base oil Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- -1 polyene hydrocarbon Chemical class 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 229920013639 polyalphaolefin Polymers 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 235000006708 antioxidants Nutrition 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000009738 saturating Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical group CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- UUNBFTCKFYBASS-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC UUNBFTCKFYBASS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical class CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Lubricants (AREA)
Abstract
The present invention provides a lubricating oil composition having excellent low temperature viscosity properties suitable for engine oils for automobiles and industries, gear oils, shock absorber oils, hydraulic fluids and it also provides a lubricating oil for internal-combustion engines formed from the composition. The lubricating oil composition comprises; a lubricating oil base (A) having a kinematic viscosity at 100 DEG C of 1 to 50 mm<2>/s and a viscosity index of not less than 80, an ethylene . propylene copolymer (B) having the following properties (B1) to (B4) such that (B1) the ethylene content is from 30 to 75 % by weight, (B2) the intrinsic viscosity eta is from 1.3 to 2.0 dl/g, (B3) the Mw/Mn is not more than 2.4 and (B4) the melting point as measured with DSC is not higher than 30 DEG C, and optionally a pour point depressant (C).
Description
Technical field
The present invention relates to contain a kind of special ethylene-propylene copolymer as the lubricating oil composition of viscosity improver of lubricating oil and the lubricating oil that is applicable to oil engine that contains said composition.
Background of invention
The viscosity of petroleum products generally has great variation along with the change of temperature,, has the temperature dependency of viscosity that is.For example, the lubricating oil that is applicable to automobile or analogue preferably has lower viscosity temperature dependency.In order to reduce the temperature dependency of viscosity, can in lubricating oil, add certain polymkeric substance of dissolving in lube base stock with as viscosity index improver.In the last few years, ethylene-propylene copolymer was widely used as viscosity index improver, in addition, also ethene-alpha-olefin copolymer had been carried out multiple improvement with the further performance (with reference to the issue of WO00/34420) of improving lubricating oil.
The general viscosity index improver that uses is so that lubricating oil can be possessed suitable viscosity when high temperature.Recently, improved by the quality of lubrication oil standard of representative is existing with the engine oil, therefore, need be used for the multipolymer of viscosity modifier especially, viscosity modifier can reduce viscosity (having good low-temperature performance) when low temperature.In the application of lubricating oil, need reduce polymer concentration as much as possible so that lubricating oil has better low-temperature performance.For above-mentioned reason,, can use the polymkeric substance of higher molecular weight also because of economic interests.But,, shear stability can occur and reduce this problem if molecular weight has increased and the polymkeric substance increasing amount has reduced.
In addition, common lubricating oil contains paraffin class mineral oil, and the paraffin composition accounts for 1～5% of total amount in the paraffin class mineral oil.Paraffin can form tabular crystal when low temperature, and can further absorb oil component with the formation tridimensional network, thereby the flowability of whole lubricating oil is reduced greatly.Use pour point reducer simultaneously, make this tabular crystal become amorphous state, to improve flowability.But, the kind difference of lube base stock, the effect of pour point reducer can differ widely, and therefore, needs to select a kind of pour point reducer that is applicable to all lube base stock.
In the application of the engine oil, gear oil (comprising ATF), hydraulic efficiency oil and the similar oil that are applicable to automobile and industry, use highly purified lube base stock, for example, the increase classification be grade (II) and oil (III) to substitute the classification that habitually in the past is widely used as lube base stock be the oil of grade (I), its objective is with existing corresponding relevant for setting up new standard and implementing the desired characteristic of environmental legislation.
Use there is a bigger problem in engine oil, and its low temperature viscosity (oil pump send the parameter of performance) that is promptly recorded by small-sized rotational viscosimeter is increasing, and low temperature viscosity is a main standard.
The inventor finds at present, and high molecular weight ethylene-α-propylene copolymer can be used as viscosity index improver, so that lubricating oil has good low-temperature performance and economic performance, but, if its molecular weight is too high, its solubleness in lube base stock can reduce, and low-temperature performance also can variation.They also find, use highly purified lube base stock can make the solubleness of high molecular weight ethylene-α-propylene copolymer that the trend of further reduction is arranged.
In this case, the inventor has carried out research unfailingly to the problems referred to above, and find by using viscosity index improver to address these problems, viscosity index improver is an ethylene propylene copolymer, its ethylene content, molecular weight, molecular weight distribution and fusing point and can select to use pour point reducer as required in specified range.So just finished the present invention.
The object of the present invention is to provide a kind of the have good low temperature viscosity performance and the lubricating oil composition of thickening capabilities, can be used for engine oil, gear oil, shock-absorber oil, the hydraulic efficiency oil of automobile and industrial application.The present invention also provides a kind of lubricating oil that is used for oil engine that is generated by said composition.
Summary of the invention
Lubricating oil composition of the present invention (AA) comprising:
The lube base stock of 80～99 weight % (A), its kinematic viscosity in the time of 100 ℃ is 1～50mm
2/ s, and viscosity index is not less than 80; And,
The ethylene-propylene copolymer of 1～20 weight % (B), it has following performance (B1)～(B4):
(B1) ethylene content is 30～75 weight %,
(B2) limiting viscosity [η] is 1.3～2.0dl/g,
(B3) Mw/Mn is not more than 2.4,
(B4) fusing point that records with DSC is not higher than 30 ℃.
In lubricating oil composition of the present invention (AA), the preferred mineral oil of selecting to have following performance (A1)～(A3) or poly-alpha-olefin are as lube base stock (A):
(A1) viscosity index is not less than 80,
(A2) saturated hydrocarbon content is not less than 90 volume %,
(A3) sulphur content is not more than 0.03 weight %.
Lubricating oil composition of the present invention (BB) comprising:
The lube base stock of 92～99.85 weight % (A), its kinematic viscosity in the time of 100 ℃ is 1～50mm
2/ s, and viscosity index is not less than 80; And,
0.1 the ethylene-propylene copolymer of～5 weight % (B), it has following performance (B1)～(B4):
(B1) ethylene content is 30～75 weight %,
(B2) limiting viscosity [η] is 1.3～2.0dl/g,
(B3) Mw/Mn is not more than 2.4,
(B4) fusing point that records with DSC is not higher than 30 ℃; With
0.05 the pour point reducer of～3 weight % (C).
In the present invention, the fusing point of the pour point reducer that records with DSC (C) preferably is not higher than-13 ℃.
The lubricating oil of the present invention that is applicable to oil engine contains lubricating oil composition (BB).
Embodiment
Below to lubricating oil composition of the present invention and be applicable to that the lubricating oil of oil engine is described.
Lubricating oil composition of the present invention (AA) contains lube base stock (A) and ethylene-propylene copolymer (B), and lubricating oil composition (BB) contains lube base stock (A), ethylene-propylene copolymer (B) and pour point reducer (C).
At first, description is the various components that comprised in the lubricating oil composition of the present invention.
Lube base stock (A)
Lube base stock used in the present invention (A) can comprise mineral oil and synthetic oil, for example the ester of poly-alpha-olefin, polyvalent alcohol and diester.
Usually use through the mineral oil of purification step, and have the grade of stipulating according to purification procedures such as dewaxing or similar step.Stipulated grade according to API (API) classification.In table 1, demonstrate the performance that is included into the lube base stock in each grade.
Table 1
| Grade | Kind | Viscosity index *1 | Saturated hydrocarbon component (volume %) *2 | Sulphur component (weight %) *3 |
| (I) *4 | Mineral oil | 80～120 | ＜90 | ＞0.03 |
| (II) | Mineral oil | 80～120 | ≥90 | ≤0.03 |
| (III) | Mineral oil | ≥120 | ≥90 | ≤0.03 |
| (IV) | Poly-alpha-olefin | |||
| (V) | Except that above-mentioned other lube base stock these | |||
*1: record according to ASTM D445 (JIS K2283)
*2: record according to ASTM D3238
*3: record according to ASTM D4294 (JIS K2541)
*4: saturated hydrocarbon component less than 90 volume %, sulphur component less than mineral oil, the saturated hydrocarbon component of 0.03 weight % be not less than 90 volume %, the sulphur component also is included in the grade (I) greater than the mineral oil of 0.03 weight %.
Poly-alpha-olefin in the table 1 is a hydrocarbon polymer, can obtain by the alpha-olefin that polymerization has an at least a starting monomer of conduct of at least 10 carbon atoms, for example, can obtain poly decene by the polymerization decylene-1.
The mineral oil that is used as lube base stock (A) among the present invention preferably through highly purified, belong to those of grade (I)～(IV), kinematic viscosity is 1～50mm in the time of preferred 100 ℃
2/ s, viscosity index are not less than 80 mineral oil or poly-alpha-olefin, more preferably through highly purified grade (II) or the mineral oil (III) of belonging to, or through highly purified, as to belong to grade (IV) poly-alpha-olefin.
Mineral oil can contain the ester and the diester of other mineral oil and synthetic oil such as poly-alpha-olefin, polyvalent alcohol, and its quantity should be not more than 20 weight %.
In the present invention, preferably have the mineral oil or the poly-alpha-olefin of following performance (A1)～(A3), as lube base stock (A).In these lube base stock, especially preferably has the mineral oil of performance (A1)～(A3).
(A1) viscosity index is not less than 80,
(A2) saturated hydrocarbon content is not less than 90 volume %,
(A3) sulphur content is not higher than 0.03 weight %.
Can measure viscosity index, saturated hydrocarbon component and sulphur component with the following method.
Viscosity index:
Measure viscosity index according to ASTM D445 (JIS K2283).
Saturated hydrocarbon component:
Measure saturated hydrocarbon content according to ASTM D3238.
The sulphur component:
Measure sulphur content according to ASTM D4294 (JIS K2541).
Its polymers of ethylene-propylene (B)
Employed ethylene-propylene copolymer (B) is the polymkeric substance that is used to improve viscosity index among the present invention.
Ethylene-propylene copolymer (B) contains the repeating unit (hereinafter being called " another kind of monomer ") that is formed by at least a monomer that is selected from cycloolefin and polyene hydrocarbon, its quantity is not more than 5 weight %, more preferably no more than 1 weight %, but still can reach purpose of the present invention.
In a preferred embodiment of the present invention, said composition does not contain polyenoid.Do not contain the polyenoid composition and have good especially thermotolerance.The also preferred ethylene-propylene copolymer of forming by ethene and propylene basically (B).
Ethylene-propylene copolymer (B) has following performance (B1), (B2), (B3) and (B4).
(B1) ethylene content
Ethylene content is generally 30～75 weight %, preferred 40～60 weight %, especially preferred 42～52 weight % in the ethylene-propylene copolymer (B).Can be according to the method described in " polymer analysis handbook " (Japanese SAC compiles and edit, the polymer analysis research grade that Kinokuniya company limited publishes), measure ethylene content in the ethylene-propylene copolymer (B) with 13C-NMR.
Ethylene content in ethylene-propylene copolymer (B) is within above-mentioned scope, and the lubricating oil composition of generation has the over-all properties of good low-temperature performance and shear stability.
(B2) limiting viscosity [η] (dl/g)
The limiting viscosity [η] of ethylene-propylene copolymer (B) is 1.3～2.0dl/g, preferred 1.4～1.9dl/g, more preferably 1.5～1.8dl/g.
When being 135 ℃, the limiting viscosity [η] of ethylene-propylene copolymer (B) in naphthalane, measures.
What generated contains ethylene-propylene copolymer (B), the lubricating oil composition of limiting viscosity [η] in above-mentioned scope, especially has the good low-temperature performance and the over-all properties of thickening properties.In addition, if the limiting viscosity of lubricating oil composition [η] in above-mentioned scope, then viscosity is very low under low temperature-low shear rate condition, and helps the pump-conveying property of lubricationpump, and therefore fuel economy loss.
(B3) molecular weight distribution
(Mw: weight-average molecular weight, Mn: number-average molecular weight) be not more than 2.4, preferred 1～2.2, Mw/Mn is an index of reflection molecular weight distribution to the Mw/Mn of ethylene-propylene copolymer (B).
In the time of 140 ℃, in orthodichlorobenzene, measure the Mw/Mn of ethylene-propylene copolymer (B) with GPC (the saturating chromatogram of gel strike-through).
If molecular weight distribution is greater than 2.4, the shear stability of lubricating oil can variation.
(B4) fusing point (Tm)
The fusing point of ethylene-propylene copolymer (B) is not higher than 30 ℃, preferably is not higher than 0 ℃, more preferably no higher than-30 ℃.
Measure the fusing point of ethylene-propylene copolymer (B) with dsc (DSC).Exactly, the sample of about 5mg is wrapped in the aluminium dish, be heated to 200 ℃, and in the time of 200 ℃, kept 5 minutes.After this, sample is cooled to-40 ℃, and in the time of-40 ℃, kept 5 minutes, then,, can determine fusing point by endothermic curve with 10 ℃/minute speed elevated temperature with 10 ℃/minute speed.
Fusing point is an interactional indication of ethylene-propylene copolymer (B) and pour point reducer (C).Importantly ethylene-propylene copolymer (B) does not contain the ethene sequence, to avoid the interaction between multipolymer (B) and the pour point reducer (C), close (for example, within-5～+ 10 ℃ of scopes of pour point reducer fusing point) of the fusing point of described ethene sequence and pour point reducer (C).
By make ethene and copolymerization of propylene with catalyzer, can prepare employed ethylene-propylene copolymer (B) among the present invention, catalyzer comprises transistion metal compound such as vanadium, zirconium or titanium, organo-aluminium compound (Organoaluminoxy based compound) and/or ionized ionic compound.For example, in the publication of WO00/34420, outlined the catalyzer that is applicable to olefinic polymerization.
Pour point reducer (C)
As the pour point reducer among the present invention, can use the polymerizable compound that has the organic acid acetic group, especially preferably have the ethene polymers of organic acid acetic group.The polyvinyl example that has the organic acid acetic group can comprise alkyl methacrylate (being total to) polymkeric substance, alkyl acrylate (being total to) polymkeric substance, fumaric acid alkyl ester (being total to) polymkeric substance, toxilic acid alkyl ester (being total to) polymkeric substance and alkylnaphthalene.
The pour point reducer (C) that preferably has following performance (C1):
(C1) fusing point of pour point reducer (C):
The fusing point of pour point reducer (C) is not higher than-13 ℃, preferably is not higher than-15 ℃, more preferably no higher than-17 ℃.
Definite method of the fusing point of pour point reducer (C) is identical with the measuring method of the fusing point of ethylene-propylene copolymer (B).
Pour point reducer (C) also has following performance (C2):
(C2) molecular weight of pour point reducer (C) (weight-average molecular weight of representing with polystyrene: Mw):
The weight-average molecular weight of pour point reducer (C) is 20,000～400,000, and is preferred 30,000～300,000, more preferably 40,000～200,000.
In the time of 40 ℃, in tetrahydrofuran solvent, measure the weight-average molecular weight of pour point reducer (C) with GPC (the saturating chromatogram of gel strike-through).
Lubricating oil composition (AA)
Lubricating oil composition of the present invention (AA) contains lube base stock (A) and ethylene-propylene copolymer (B).The lubricator composition contains lube base stock (A) and ethylene-propylene copolymer (B), the amount of lube base stock (A) is 80～99 weight %, be preferably 85～95 weight %, the amount of ethylene-propylene copolymer (B) is 1～20 weight %, is preferably 5～15 weight %.In composition (AA), the total amount of lube base stock (A) and ethylene-propylene copolymer (B) is composition 100 weight %.
Lubricating oil composition has cryogenic dependence and good low-temperature performance.Lubricating oil composition can use like this, perhaps lubricating oil composition can mix mutually with lube base stock, pour point reducer or analogue, with preparation hereinafter described lubricating oil composition (BB), and then generation is applicable to the lubricating oil composition of various lubricating oil purposes.Other lube base stock except lube base stock (A) is can blended.For lubricating oil composition (AA), can suitably add described hereinafter additive such as pour point reducer, antioxidant, detergent dispersant, extreme pressure agent, antifoams, rust-preventive agent, inhibiter and analogue as required.
Lubricating oil composition (BB)
Lubricating oil composition of the present invention (BB) contains lube base stock (A), ethylene-propylene copolymer (B) and pour point reducer (C).Lubricating oil composition contains lube base stock (A), ethylene-propylene copolymer (B) and pour point reducer (C), the amount of lube base stock (A) is 92～99.85 weight %, be preferably 95～99.7 weight %, 97～99.5 weight % more preferably, the amount of ethylene-propylene copolymer (B) is 0.1～5 weight %, be preferably 0.2～3 weight %, 0.4～2 weight % more preferably, the amount of pour point reducer (C) is 0.05～3 weight %, be preferably 0.1～2 weight %, more preferably 0.1～1 weight %.The total amount of lube base stock (A), ethylene-propylene copolymer (B) and pour point reducer (C) is 100 weight %.
The lube base stock that adds in the lubricating oil composition (AA) can be identical with contained lube base stock in the lubricating oil composition (AA), more can preferably have the lube base stock of above-mentioned (A1)～(A3) performance.
Lubricating oil composition (BB) contains lube base stock (A), ethylene-propylene copolymer (B) and pour point reducer (C), and it has cryogenic dependence and good low-temperature performance, and especially it has low viscosity under the condition of low temperature-low shear rate.
Additive
Lubricating oil composition of the present invention contains lube base stock (A), ethylene-propylene copolymer (B) and optional pour point reducer (C) and additive such as the anti-oxidant utmost point, detergent dispersant, extreme pressure agent, defoamer, rust-preventive agent, inhibiter and analogue, and additive can add in the composition as required.
The embodiment of antioxidant can comprise phenol antioxidant such as 2,6-two-tertiary butyl-4-methylphenol and analogue, amine antioxidants such as dioctyl diphenylamine and analogue.
The embodiment of detergent dispersant can comprise sulfonation class detergent dispersant such as calcium sulfonate and magnesium sulfonate, phenates, salicylate, succinimide and benzylamine.
The embodiment of extreme pressure agent can comprise sulfuration oil ﹠ fat, olefine sulfide, sulfide, phosphoric acid salt, phosphite, phosphate amine salt and phosphorous acid amine salt.
The embodiment of defoamer can comprise silicon class antifoams such as dimethyl siloxane and silica gel dispersion agent, alcohols and ester defoamer.
The embodiment of rust-preventive agent can comprise carboxylic acid, carboxylate salt, ester and phosphoric acid.
The embodiment of inhibiter can comprise benzotriazole, its derivative and thiazole compound.
Preparation process
Lubricating oil composition of the present invention (AA) and (BB) can be by using general known method mixes in lube base stock (A) or dissolve ethylene-propylene copolymer (B), pour point reducer (C), the more optional additive chosen wantonly prepare.
Lubricating oil composition (BB) can also prepare by adding pour point reducer (C) and optional lube base stock in lubricating oil composition (AA).In this process, the lube base stock that is added in the lubricating oil composition (AA) can be identical with contained lube base stock (A) in the lubricating oil composition (AA), also can preferably have those lube base stock of performance (A1)～(A3).
Effect
Lubricating oil composition of the present invention has the low viscosity of defined in the SAE viscosity criterion under the condition of low temperature and low shear rate, also have good pump-conveying property, can be used as lubricating oil such as the engine oil and the analogue that are used for oil engine.
Embodiment
Below, by the present invention having been carried out more detailed description with reference to following embodiment.With following method the different physical characteristics among the embodiment is measured.
Ethylene content:
In the time of 120 ℃, pulse width with 45 °, 5.5 the pulse repetition time of second, in the mixed solvent of orthodichlorobenzene and benzene-d6 (orthodichlorobenzene/benzene-d6=3/1～4/1 (volume ratio)), ethylene content is measured with LA500 nuclear magnetic resonance analyser (making) by JEOL.
Limiting viscosity [η]:
In naphthalane, limiting viscosity [η] is measured in the time of 135 ℃.
Mw/Mn：
In the time of 140 ℃, in the orthodichlorobenzene solvent, Mw/Mn is measured with GPC (the saturating chromatogram of gel strike-through).
Kinematic viscosity in the time of 100 ℃ (K.V.):
Measure kinematic viscosity according to ASTM D445.In the present embodiment, the K.V. with sample oil is adjusted to 11mm
2/ s.
Small-sized rotational viscosimeter (MRV) viscosity:
According to ASTM D3829 and D4684, in the time of-35 ℃, measure viscosity.The pump-conveying property of oil pump when MRV viscosity can be used for estimating low temperature.When the numerical value of MRV viscosity hour, then low-temperature performance is better.
Cold cranking simulator (CCS) viscosity:
According to ASTM D2602, when-25 ℃ and-30 ℃, measure CCS viscosity.Sliding capability (starting performance) when CCS viscosity can be used for estimating low temperature in the bent axle.When the numerical value of CCS viscosity hour, then low-temperature performance is better.
Shear stability index (SSI):
Measure SSI according to ASTM D3945.SSI is a kind of index of the kinematic viscosity loss that caused by the molecular chain cracking, and the copolymer component in the lubricating oil can cause the molecular chain cracking after being sheared in the metal slide unit.When SSI numerical value was big, then loss was just big more.
Polymerization embodiment 1～4
In each embodiment, the successive polymerization device that will be equipped with the 2L volume of agitating vane with nitrogen thoroughly purifies, and adds the hexane of 1L through dehydration and purification, and feeds the sesquialter ethylaluminium chloride (Al (C of 8.0mmol/L in continuous 1 hour with the speed of 500mL/h
2H
5)
1.5Cl
1.5) hexane solution, it feeds the VO (OC of 0.8mmol/L continuously as catalyzer with the speed of 500mL/h thereafter
2H
5) Cl
2Hexane solution, and feed hexane continuously with the speed of 500mL/h.Simultaneously, draw polymeric solution continuously, so that the polymeric solution amount in the polymerizer remains 1L from the top of polymerizer.
Next use bubbler tube, with the speed feeding ethene of 180L/h, with the speed feeding propylene of 120L/h, with the speed feeding hydrogen of 1.5～5.5L/h.Make the refrigerant carrier at a chuck internal recycle that is contained in the polymerizer outside, copolymerization is carried out in the time of 15 ℃.
Reaction is carried out under these conditions, and prepares the polymeric solution that contains ethylene-propylene copolymer therefrom.With hydrochloric acid with the polymeric solution deliming that is generated after, add a large amount of methyl alcohol again to be settled out ethylene-propylene copolymer.Thereafter, under reduced pressure with ethylene-propylene copolymer 130 ℃ the time dry 24 hours.The polymkeric substance that is generated has performance as shown in table 2 below.
Table 2
| Polymerization embodiment | ||||
| 1 | 2 | 3 | 4 | |
| Polymerizing condition ethene (liter/time) propylene (liter/time) hydrogen (liter/time) | 180 120 5.5 | 180 120 3.5 | 180 120 2.0 | 180 120 1.5 |
| Polymer performance ethylene content (weight %) [η] (dl/g) the Mw/Mn fusing point (℃) | 49 1.20 2.0 ＜-40 * | 49 1.45 1.9 ＜-40 | 50 1.84 2.0 ＜-40 | 51 2.18 2.1 ＜-40 |
*: under-40 ℃ or higher temperature condition, do not observe fusing point.
Polymerization embodiment 5
The stainless steel autoclave that will be equipped with the 2L volume of agitating vane with nitrogen purifies up hill and dale, adds the heptane of 900mL in the time of 23 ℃.Under agitating vane rotation and ice-cooled condition, in this autoclave, add the propylene of 13NL and the hydrogen of 100mL.Next autoclave is heated to 70 ℃, and pressurizes, make total pressure reach 6KG with ethene.When the internal pressure of autoclave reaches 6KG, feed the hexane solution 1.0mL of the 1.0mmol/mL tri-butyl aluminum of 1.0mL by pressurized nitrogen.Under stress feed the toluene solution of 3ml in autoclave continuously, this solution contains 0.02mM according to triphenylcarbenium (four-pentafluorophenyl group) borate of B and [dimethyl (tert-butylamides) (tetramethyl--η of 0.0005mmol
5-cyclopentadienyl) silane] titanium dichloride, and the beginning polymerization., the temperature of autoclave controlled 5 minute, make internal temperature reach 70 ℃, and directly feed ethene, make pressure reach 6kg thereafter.After the auto-polymerization reaction beginning 5 minutes, use pump in autoclave, to feed the methyl alcohol of 5mL, polyreaction is stopped.Then, autoclave is decompressed to normal atmosphere.The methyl alcohol that under agitation in reaction soln, adds 3L.600 holders, under 130 ℃ with the solvent seasoning that contains polymkeric substance that generated 13 hours, to prepare 31 gram ethylene-propylene copolymers.Ethylene content is 47 weight % in the polymkeric substance that is generated, and [η] is 1.6dl/g, and Mw/Mn is 2.1, and fusing point is lower than-40 ℃ (not observing fusing point under-40 ℃ or higher temperature).
Embodiment 1
As lube base stock (A) (base oil), this neutral mineral oil classification is grade (II) with 120 neutral mineral oils of 87.85 weight % (TM, ESSO company limited makes), and its kinematic viscosity is 4.60mm in the time of 100 ℃
2/ s, viscosity index is 114, saturated hydrocarbon component is 99 volume %, and the sulphur component is not higher than 0.001 weight %.With the ethylene-propylene copolymer (B) of 0.85 weight % of preparation among the polymerization embodiment 2 as the ACLUBE 146 of viscosity index improver, 0.3 weight %
TM(Sanyo chemical industry company limited makes) is as the detergent dispersant LZ 20003C of pour point reducer (C) and 11.0 weight %
TM(Lubrizol limited-liability company makes) prepares lubricating oil composition and estimates its lubricants performance.
The result is as shown in table 3.
Embodiment 2
Repeat the process of embodiment 1, except making viscosity index improver (B) with the ethylene-propylene copolymer of 0.76 prepared among the polymerization embodiment 5 weight %.The result is as shown in table 3.
Embodiment 3
Repeat the process of embodiment 1, except making viscosity index improver (B) with the ethylene-propylene copolymer of 0.70 prepared among the polymerization embodiment 3 weight %.The result is as shown in table 3.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Blended ethylene-propylene copolymer (B) | Polymerization embodiment 2 | Polymerization embodiment 5 | Polymerization embodiment 3 |
| Composition (weight %) lube base stock (A) (base oil) ethylene-propylene copolymer (B) *1 pour point reducer ACLUBE146 *2 detergent dispersants (LZ 20003C) | 87.85 0.85 0.30 11.00 | 87.94 0.76 0.30 11.00 | 88.00 0.70 0.30 11.00 |
| *[η] of 1 ethylene-propylene copolymer (B) (dl/g) *The fusing point of 2 pour point reducers (C) (℃) (℃) *The weight-average molecular weight (Mw) of 2 pour point reducers (C) | 1.45 -19.0 56100 | 1.60 -19.0 56100 | 1.84 -19.0 56100 |
| Kinematic viscosity (mm in the time of Run Huayouxingneng @100 ℃ 2/ s) ((MR viscosity (mPas) SSI during @-35 ℃ of mPas) of the CCS viscosity during @-30 ℃ of mPas) of the CCS viscosity @-25 ℃ the time | 11.02 3090 6200 32500 41 | 10.96 3050 6120 29600 44 | 11.00 3010 6060 30650 46 |
@XX ℃ of symbol “ " measurement carried out when being illustrated in XX ℃.
Hereinafter, symbol “ @XX ℃ " also herewith.
Embodiment 4
With 120 neutral mineral oils of 87.37 weight % (ESSO company limited makes) as the ethylene-propylene copolymer of 0.83 weight % of preparation among lube base stock (A) (base oil), the polymerization embodiment 2 ACLUBE 146 as viscosity index improver (B), 0.3 weight %
TM(Sanyo chemical industry company limited makes) is as the detergent dispersant LZ 20003C of pour point reducer (C) and 11.5 weight %
TM(Lubrizol limited-liability company makes) prepares lubricating oil composition and estimates its lubricants performance.
The result is as shown in table 4.
Embodiment 5
Repeat the process of embodiment 4, except 120 neutral mineral oils (ESSO company limited makes) and the ethylene-propylene copolymer of 0.74 weight % with 87.46 prepared among the polymerization embodiment 5 weight % are made viscosity index improver (B).The result is as shown in table 4.
Embodiment 6
Repeat the process of embodiment 4, except 120 neutral mineral oils (ESSO company limited makes) and the ethylene-propylene copolymer of 0.68 weight % with 87.52 prepared among the polymerization embodiment 3 weight % are made viscosity index improver (B).The result is as shown in table 4.
Embodiment 7
Repeat the process of embodiment 4, except making pour point reducer (C) with ACLUBE 136 (TM, Sanyo chemical industry company limited makes).
The result is as shown in table 4.
Embodiment 8
Repeat the process of embodiment 5, except making pour point reducer (C) with ACLUBE 136 (TM, Sanyo chemical industry company limited makes).
The result is as shown in table 4.
Embodiment 9
Repeat the process of embodiment 6, except making pour point reducer (C) with ACLUBE 136 (TM, Sanyo chemical industry company limited makes).
The result is as shown in table 4.
Table 4
| Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Blended ethylene-propylene copolymer (B) | Polymerization embodiment 2 | Polymerization embodiment 5 | Polymerization embodiment 3 |
| Composition (weight %) lube base stock (A) (base oil) ethylene-propylene copolymer (B) *1 pour point reducer (C) ACLUBE 146 *2 pour point reducers (C) ACLUBE 136 *2 detergent dispersants (LZ 20003C) | 87.37 0.83 0.30 11.50 | 87.46 0.74 0.30 11.50 | 87.52 0.68 0.30 11.50 |
| *[η] of 1 ethylene-propylene copolymer (B) (dl/g) *The fusing point of 2 pour point reducers (C) (℃) (℃) *The weight-average molecular weight (Mw) of 2 pour point reducers (C) | 1.45 -19.0 56100 | 1.60 -19.0 56100 | 1.84 -19.0 56100 |
| Kinematic viscosity (mm in the time of Run Huayouxingneng @100 ℃ 2/ s) (MR viscosity (mPas) SSI during @-35 ℃ of mPas) of the CCS viscosity @-25 ℃ the time | 10.88 3060 29170 41 | 10.79 3040 28280 44 | 10.72 3040 28820 46 |
Table 4 (continuing)
| Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Blended ethylene-propylene copolymer (B) | Polymerization embodiment 2 | Polymerization embodiment 5 | Polymerization embodiment 3 |
| Composition (weight %) lube base stock (A) (base oil) ethylene-propylene copolymer (B) *1 pour point reducer (C) ACLUBE 146 *2 pour point reducers (C) ACLUBE 136 *2 detergent dispersants (LZ 20003C) | 87.37 0.83 0.30 11.50 | 87.46 0.74 0.30 11.50 | 87.52 0.68 0.30 11.50 |
| *[η] of 1 ethylene-propylene copolymer (B) (dl/g) *The fusing point of 2 pour point reducers (C) (℃) (℃) *The weight-average molecular weight (Mw) of 2 pour point reducers (C) | 1.45 -18.1 100200 | 1.60 -18.1 100200 | 1.84 -18.1 100200 |
| Kinematic viscosity (mm in the time of Run Huayouxingneng @100 ℃ 2/ s) (MR viscosity (mPas) SSI during @-35 ℃ of mPas) of the CCS viscosity @-25 ℃ the time | 10.90 3050 28640 42 | 10.91 3040 28950 45 | 10.76 3010 29060 46 |
The comparative example 1
Repeat the process of embodiment 4, except 120 neutral mineral oils (ESSO company limited makes) and the ethylene-propylene copolymer of 1.00 weight % with 87.70 prepared among the polymerization embodiment 1 weight % are done the viscosity index improver (B).The result is as shown in table 5.
The comparative example 2
Repeat the process of embodiment 1, except 120 neutral mineral oils (ESSO company limited makes) and the ethylene-propylene copolymer of 0.61 weight % with 88.09 prepared among the polymerization embodiment 4 weight % are done the viscosity index improver (B).The result is as shown in table 5.
Table 5
| The comparative example 1 | The comparative example 2 | |
| Blended ethylene-propylene copolymer (B) | Polymerization embodiment 1 | Polymerization embodiment 4 |
| [η] of composition (% by weight) lube base stock (A) (base oil) ethylene-propylene copolymer (B) ethylene-propylene copolymer (B) be pour-point depressant (C) ACLUBE 146 detergent dispersants (LZ 20003C) (dl/g) | 87.70 1.00 1.20 0.30 11.00 | 88.09 0.61 2.18 0.30 11.00 |
| Kinematic viscosity (mm in the time of Run Huayouxingneng @100 ℃ 2/ s) ((MR viscosity (mPas) SSI during @-35 ℃ of mPas) of the CCS viscosity during @-30 ℃ of mPas) of the CCS viscosity @-25 ℃ the time | 10.92 3120 6280 52500 30 | 10.98 2950 6010 48600 57 |
The comparative example 3
With classification be grade (II), kinematic viscosity is 4.60mm 100 ℃ the time
2The mineral oil of/s, 87.22 weight % (ESSO company limited makes) is as the ethylene-propylene copolymer of 0.98 weight % of preparation among lube base stock (A) (base oil), the polymerization embodiment 1 ACLUBE146 as viscosity index improver (B), 0.3 weight %
TM(Sanyo chemical industry company limited makes) is as the detergent dispersant LZ 20003C of pour point reducer (C) and 11.5 weight %
TM(Lubrizol limited-liability company makes) prepares lubricating oil composition and estimates its lubricants performance.
The result is as shown in table 6.
The comparative example 4
Repeat comparative example 3 process, except with prepared among the polymerization embodiment 4, kinematic viscosity is 4.60mm 100 ℃ the time
2The mineral oil of the 87.61 weight % of/s (ESSO company limited makes) and the ethylene-propylene copolymer of 0.59 weight % are done outside the viscosity index improver (B).The result is as shown in table 6.
The comparative example 5
Repeat comparative example 3 process, except using ACLUBE 136
TM(Sanyo chemical industry company limited makes) done outside the pour point reducer (C).
The result is as shown in table 6.
The comparative example 6
Repeat comparative example 4 process, except using ACLUBE 136
TM(Sanyo chemical industry company limited makes) done outside the pour point reducer (C).
The result is as shown in table 6.
Table 6
| The comparative example 3 | The comparative example 4 | |
| Blended ethylene-propylene copolymer (B) | Polymerization embodiment 1 | Polymerization embodiment 4 |
| Composition (weight %) lube base stock (A) (base oil) ethylene-propylene copolymer (B) *1 pour point reducer (C) ACLUBE 146 *2 pour point reducers (C) ACLUBE 136 *2 detergent dispersants (LZ 20003C) | 87.22 0.98 0.30 11.50 | 87.61 0.59 0.30 11.50 |
| *[η] of 1 ethylene-propylene copolymer (B) (dl/g) *The fusing point of 2 pour point reducers (C) (℃) (℃) *The weight-average molecular weight (Mw) of 2 pour point reducers (C) | 1.20 -19.0 56100 | 2.18 -19.0 56100 |
| Kinematic viscosity (mm in the time of Run Huayouxingneng @100 ℃ 2/ s) (MR viscosity (mPas) SSI during @-35 ℃ of mPas) of the CCS viscosity @-25 ℃ the time | 10.79 3120 52870 30 | 10.88 2950 48650 57 |
Table 6 (continuing)
| The comparative example 5 | The comparative example 6 | |
| Blended ethylene-propylene copolymer (B) | Polymerization embodiment 1 | Polymerization embodiment 4 |
| Composition (weight %) lube base stock (A) (base oil) ethylene-propylene copolymer (B) *1 pour point reducer (C) ACLUBE 146 *2 pour point reducers (C) ACLUBE 136 *2 detergent dispersants (LZ 20003C) | 87.22 0.98 0.30 11.50 | 87.61 0.59 0.30 11.50 |
| *[η] of 1 ethylene-propylene copolymer (B) (dl/g) *The fusing point of 2 pour point reducers (C) (℃) (℃) *The weight-average molecular weight (Mw) of 2 pour point reducers (C) | 1.20 -18.1 100200 | 2.18 -18.1 100200 |
| Kinematic viscosity (mm in the time of Run Huayouxingneng @100 ℃ 2/ s) (MR viscosity (mPas) SSI during @-35 ℃ of mPas) of the CCS viscosity @-25 ℃ the time | 10.85 3150 54330 30 | 10.91 2930 51740 57 |
Embodiment 10
Repeat the process of embodiment 4, except doing outside the pour point reducer (C) with ACLUBE 133 (TM, Sanyo chemical industry company limited makes).
The result is as shown in table 7.
Embodiment 11
Repeat the process of embodiment 5, except doing outside the pour point reducer (C) with ACLUBE 133 (TM, Sanyo chemical industry company limited makes).
The result is as shown in table 7.
Embodiment 12
Repeat the process of embodiment 6, except doing outside the pour point reducer (C) with ACLUBE 133 (TM, Sanyo chemical industry company limited makes).
The result is as shown in table 7.
Embodiment 13
Repeat the process of embodiment 4, except doing outside the pour point reducer (C) with VISCOPLX 1-156 (TM, Roh Max company limited makes).
The result is as shown in table 7.
Embodiment 14
Repeat the process of embodiment 5, except doing outside the pour point reducer (C) with VISCOPLX 1-156 (TM, Roh Max company limited makes).
The result is as shown in table 7.
Embodiment 15
Repeat the process of embodiment 6, except doing outside the pour point reducer (C) with VISCOPLX 1-156 (TM, Roh Max company limited makes).
The result is as shown in table 7.
Table 7
| Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Blended ethylene-propylene copolymer (B) | Polymerization embodiment 2 | Polymerization embodiment 5 | Polymerization embodiment 3 |
| Composition (weight %) lube base stock (A) (base oil) ethylene-propylene copolymer (B) *1 pour point reducer (C) ACLUBE 133 *2 pour point reducers (C) VISCOPLX 1-156 *2 detergent dispersants (LZ 20003C) | 87.37 0.83 0.30 11.50 | 87.46 0.74 0.30 11.50 | 87.52 0.68 0.30 11.50 |
| *[η] of 1 ethylene-propylene copolymer (B) (dl/g) *The fusing point of 2 pour point reducers (C) (℃) (℃) *The weight-average molecular weight (Mw) of 2 pour point reducers (C) | 1.45 -11.4 418000 | 1.60 -11.4 418000 | 1.84 -11.4 418000 |
| Kinematic viscosity (mm in the time of Run Huayouxingneng @100 ℃ 2/ s) (MR viscosity (mPas) SSI during @-35 ℃ of mPas) of the CCS viscosity @-25 ℃ the time | 10.91 3090 42870 42 | 10.88 3060 41650 45 | 10.82 3050 42330 47 |
Table 7 (continuing)
| Embodiment 13 | Embodiment 14 | Embodiment 15 | |
| Blended ethylene-propylene copolymer (B) | Polymerization embodiment 2 | Polymerization embodiment 5 | Polymerization embodiment 3 |
| Composition (weight %) lube base stock (A) (base oil) ethylene-propylene copolymer (B) *1 pour point reducer (C) ACLUBE133 *2 pour point reducers (C) VISCOPLX 1-156 *2 detergent dispersants (LZ 20003C) | 87.37 0.83 0.30 11.50 | 87.46 0.74 0.30 11.50 | 87.52 0.68 0.30 11.50 |
| *[η] of 1 ethylene-propylene copolymer (B) (dl/g) *The fusing point of 2 pour point reducers (C) (℃) (℃) *The weight-average molecular weight (Mw) of 2 pour point reducers (C) | 1.45 -8.7 75600 | 1.60 -8.7 75600 | 1.84 -8.7 75600 |
| Kinematic viscosity (mm in the time of Run Huayouxingneng @100 ℃ 2/ s) (MR viscosity (mPas) SSI during @-35 ℃ of mPas) of the CCS viscosity @-25 ℃ the time | 10.94 3080 44740 42 | 10.80 3060 43880 44 | 10.77 3010 44180 46 |
Claims (3)
1. a lubricating oil composition (BB), it comprises:
The lube base stock of 92～99.85 weight % (A), the kinematic viscosity in the time of its 100 ℃ is 1～50mm
2/ s, viscosity index is not less than 80, this lube base stock (A) also has following feature: (A1) viscosity index is not less than 80, (A2) saturated hydrocarbon content be not less than 90 volume % and (A3) sulphur content be not higher than 0.03 weight %;
0.1 the ethylene-propylene copolymer of～5 weight % (B), it has following performance (B1)～(B4):
(B1) ethylene content is 30～75 weight %,
(B2) limiting viscosity [η] is 1.3～2.0dl/g,
(B3) Mw/Mn be not more than 2.4 and
(B4) fusing point that records with DSC is not higher than 30 ℃; With
0.05 recording with difference formula scanning calorimetry, the pour point reducer of～3 weight % (C), the fusing point of this pour point reducer (C) be not higher than-13 ℃.
2. lubricating oil composition as claimed in claim 1 (BB), wherein said lube base stock (A) is a mineral oil.
3. lubricating oil that is applicable to oil engine, this lubricating oil contains claim 1 or 2 described lubricating oil compositions (BB).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP327750/2002 | 2002-11-12 | ||
| JP2002327750 | 2002-11-12 | ||
| JP353129/2002 | 2002-12-04 | ||
| JP352240/2002 | 2002-12-04 |
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| CN1711344A CN1711344A (en) | 2005-12-21 |
| CN1333057C true CN1333057C (en) | 2007-08-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2003801029420A Expired - Lifetime CN1333057C (en) | 2002-11-12 | 2003-11-11 | Lubricating oil composition and internal combustion engine oil |
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| CN (1) | CN1333057C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8022024B2 (en) * | 2007-06-28 | 2011-09-20 | Chevron U.S.A. Inc. | Functional fluid compositions |
| EP2227522A1 (en) * | 2007-11-28 | 2010-09-15 | Shell Internationale Research Maatschappij B.V. | Gasoline compositions |
| WO2010027019A1 (en) | 2008-09-05 | 2010-03-11 | Ntn株式会社 | Grease composition, and roller bearing and universal joint packed with said grease composition |
| CN101392207B (en) * | 2008-10-13 | 2011-12-07 | 深圳海润德石化技术有限公司 | lubricating oil viscosity index improver |
| CN102660359B (en) * | 2012-04-06 | 2013-10-23 | 大连海事大学 | SF/CD general internal combustion engine oil composition, preparation thereof and application thereof |
| US10077412B2 (en) * | 2014-03-28 | 2018-09-18 | Mitsui Chemicals, Inc. | Viscosity modifier for lubricating oils, additive composition for lubricating oils, and lubricating oil composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329656A (en) * | 1998-12-09 | 2002-01-02 | 三井化学株式会社 | Viscosity modifier for lubricating oil and lubricating oil composition |
| CN1346398A (en) * | 1999-03-30 | 2002-04-24 | 三井化学株式会社 | Viscosity regulator for lubricating oil and lubricating oil composition |
| CN1396304A (en) * | 2002-06-21 | 2003-02-12 | 郭福春 | Process for preparing high-performance Ni-P alloy solution for chemical plating |
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2003
- 2003-11-11 CN CNB2003801029420A patent/CN1333057C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329656A (en) * | 1998-12-09 | 2002-01-02 | 三井化学株式会社 | Viscosity modifier for lubricating oil and lubricating oil composition |
| CN1346398A (en) * | 1999-03-30 | 2002-04-24 | 三井化学株式会社 | Viscosity regulator for lubricating oil and lubricating oil composition |
| CN1396304A (en) * | 2002-06-21 | 2003-02-12 | 郭福春 | Process for preparing high-performance Ni-P alloy solution for chemical plating |
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| CN1711344A (en) | 2005-12-21 |
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