CA2316997A1 - Use of polyalfaolefins (pao) derived from 1-dodecene or 1-tetradecene to improve thermal stability in engine oil in an internal combustion engine - Google Patents

Abstract

The present invention relates to compositions of automotive engine oils using synthetic polyalphaolefins derived from olefins other than 1-decene, especially 1-dodecene, to improve engine oil performance, as demonstrated by the severe Volkswagen T-4, Volkswagen TDI, and Sequence IIIE tests.

Description

r USE OF POLYALFAOLEFINS (PAO) DERIVED FROM 1-DODECENE OR 1-TETRADECENE TO
IMPROVE THERMAL
STABILTTY IN ENGINE OIL IN AN INTERNAL COMBUSTION ENGWE

FIELD OF THE INVENTION
s The present invention relates to compositions of automotive engine oils using s synthetic poly alpha olefins derived from olefins other than 1-decene, ~ especially 1-dodecene and 1-tetradecene, to improve engine oil performance, s as demonstrated by the severe Volkswagen T-4, Volkswagen TDI, and s Sequence IIIE tests.
o BACKGROUND OF THE INVENTION
~ Today's automobiles tend to have smaller, more demanding engines ~2 operating at higher temperatures. Thus, the engine oil has to function in an 13 increasingly severe environment while meeting fuel economy demands.
14 Besides changes in the additive package, increasingly synthetic base oils are.
15 being used instead of conventional mineral oils. Of the synthetic oils, poly ~s alpha olefins (PAO) are among the most popular.
17 PAO is manufactured by oligomerization of linear alpha olefin followed by ~s hydrogenation to remove unsaturated moieties and fractionation to obtain the s desired product slate. 1-decene is the most commonly used alpha olefin in 2o the manufacture of PAO, but 1-dodecene and 1-tetradecene can also be 2~ used. PAO's are commonly categorized by the numbers denoting the 22 approximate viscosity in centistokes of the PAO at 100°C. It is known that 2a PAO 2, PAO 2.5, PAO 4, PAO 5, PAO 6, PAO 7, PAO 8, PAO 9 and PAO 10 24 and combinations thereof can be used in engine oils. The most common of 2s these are PAO 4, PAO 6 and PAO 8.

Conventionally, base oils of lubricating viscosity used in motor oil 2 compositions may be mineral oil or synthetic oils of viscosity suitable for use 3 in the crankcase of an internal combustion engine. Crankcase base oils ordinarily have a viscosity of about 1300 cSt at 0°F (-18°C) to 24 cSt at 210°F
s (99°C). The base oils may be derived from synthetic or natural sources.
s Mineral oil for use as the base oil in this invention includes paraffinic, 7 naphthenic and other oils that are ordinarily used in lubricating oil s compositions. Synthetic oils include both hydrocarbon synthetic oils and 9 synthetic esters.
o Although the common 1-decene based PAO 4, 6 and 8 offer better ~ performance than mineral oil based engine oils, they encounter difficulties ~2 when subjected to the severe PV 1449, CEC L-78-T-96 and Sequence IIIE
~3 tests. The PV 1449 and Sequence IIIE tests evaluate fully formulated engine 4 oils with respect to high temperature oxidative stability and piston deposits.
~s The CEC L-78-T-96 test evaluates fully formulated engine oils with respect to s piston cleanliness and piston ring sticking. The PV 1449 and CEC L-78-T-96 7 tests will be referred to hereinafter as the Volkswagen T-4. and TDI engine ~ s tests, respectively.
s ft has been found to be difficult to blend an engine oil of the desired OW30 2o viscosity grade based on PAO 4 and 6 that successfully completes the TDI
2~ test. Repeatedly, it was found that too low oil pressure caused the engine to 22 fail from 2 to 8 hours before the end of the test. In the T-4 test, it was found 23 that the increase in engine oil viscosity resulting in engine failure during the 24 test was related to oil oxidation stability and volatility. To pass the T-4 test, it 2s was found that the PAO 4/6 based engine oil requires large quantities of 2s expensive anti-oxidants. The other way to obtain PAO 4/6 based oil which 27 passes the T-4 test is to use an expensive fully synthetic oil.

The Volkswagen T-4 and TDI tests have recently become an important 2 measure of engine lubrication oil quality under very severe conditions. The s Sequence 111E test is analogous to a T-4 test but is specifically developed for ~ 4 U.S. built engines. The T-4 and Sequence IIIE tests are for gasoline engines and the TDI test is for diesel engines. They replicate the severe engine s conditions put on motor lubrication oil by sustained, very high speed driving, 7 as on the German Autobahn. What is needed is a PAO based oil which is s able to successfully complete severe engine tests such as the Volkswagen 9 T-4 and TDl tests and the Sequence IIIE test without having to use large o quantities of anti-oxidants or a fully synthetic oil.
11 Surprisingly, it has been found that lubrication oils based on alpha olefins ~2 having at least 12 carbons, for example, 1-dodecene, and that have ~s approximate viscosities at 100°C of from 3.5 to 8.5 centistokes successfully 4 pass the T-4 and TDI tests with PAO based oil weight percentages much s lower than previously achieved. This represents a major development in the s search for an economical lubrication oil that is well suited for modern driving ~ conditions.
~8 SUMMARY OF THE INVENTION
19 In one embodiment, the present invention relates to the use of PAO derived 2o from 1-dodecene or 1-tetradecene as the base oil, or a component of the 2~ base oil, of an engine oil for the purpose of improving the high temperature 22 stability of the engine oil when compared with the use of a 1-decene derived 23 PAO.
24 In another embodiment, the present invention relates to the use of PAO
2s derived from 1-dodecene or 1-tetradecene as the base oil, or a component of 2s the base oil, of an engine oil comprised of base oil, dispersants, detergents, 2~ oxidation inhibitors, foam inhibitors, anti-wear agents and at least one ~j._ ~ viscosity index improver, for the purpose of improving the high temperature 2 stability of the engine oil to least the point at which the engine oil is able to 3 pass the VW T-4, VW TDI, or Sequence IIIE tests.
4 In a preferred embodiment of either of the above embodiments, the base oil is s from 15 to 85% of the engine oil and at feast 15% of the base oil is derived s from 1-dodecene or 1-tetradecene.
7 In another preferred embodiment of the above embodiments, the PAO is from s 50 to 85% of the base oil for OW-xx SAE viscosity grade oils where xx =
g 20-50, is from 15 to 50% of the base oil for 5W-xx SAE viscosity grade oils ~ o where xx = 20-50, or is from 5 to 35% of the base oil for 1 OW-xx SAE
viscosity grade oils where xx = 20-50.
~2 In still another embodiment, the present invention relates to an engine oil 13 having a SAE viscosity grade of OW-xx where xx denotes 20-40 comprised of 14 from 15 to 85% base oil having from 50 to 85% PAO at least 15% of which is ~5 derived from 1-dodecene or 1-tetradecene, from 0 to 20% of at least one ashless dispersant; from 0 to 30% of detergent; from 0 to 5% of at least one anti-wear agent; from 0 to 10% of at least one oxidation inhibitor; from 0 to 1 % of at least one foam inhibitor; and from 0 to 20% of at least one viscosity index improver.
2o In yet another embodiment, the present invention relates to an engine oil 2~ having a SAE viscosity grade of 5W-xx where xx denotes 20-40 comprised of 22 from 15 to 85% base oil having from 15 to 50% PAO at least 15% of which is 2s derived from 1-dodecene or 1-tetradecene, from 0 to 20% of at least one 24 ashless dispersant; from 0 to 30% of detergent; from 0 to 5% of at least one 2s anti-wear agent; from 0 to 10% of at least one oxidation inhibitor; from 0 to 2s 1 % of at least one foam inhibitor; and from 0 to 20% of at least one viscosity 2~ index improver.

In still another embodiment, the present invention relates to an engine oil 2 having a SAE viscosity grade of 10W-xx where xx denotes 20-50 comprised s of from 15 to 85% base oil having from 5 to 35% PAO at least 15% of which is ~ 4 derived from 1-dodecene or 1-tetradecene, from 0 to 20% of at least one ashless dispersant; from 0 to 30% of detergent; from 0 to 5% of at least one s anti-wear agent; from 0 to 10% of at least one oxidation inhibitor; from 0 to 1 % of at least one foam inhibitor; and from 0 to 20% of at least one viscosity index improver.
s In a preferred embodiment of any of the above embodiments, the PAO
~o derived from 1-dodecene or 1-tetradecene has an approximate viscosity at 100°C of from 3.5 to 9.5 centistokes.
~2 In a more preferred embodiment of the above embodiment, the PAO derived 13 from 1-dodecene or 1-tetradecene has an approximate viscosity at 100°C of approximately 5 centistokes or approximately 7 centistokes.
~5 BRIEF DESCRIPTION OF THE DRAWINGS
~s In order to assist the understanding of this invention, reference will now be ~ made to the appended drawings. The drawings are exemplary only, and 8 should not be construed as limiting the invention. .
s Figure 1 is a graph comparing the absolute and relative T-4 viscosity 2o increases in PAO 6 and PAO 5l7 based motor oil in an experiment the 2~ conditions of which are described in Example 5.
22 Figure 2 is a graph comparing the absolute and relative T-4 viscosity 2s increases in PAO 4, PAO 5 and PAO 6 based motor oif in an experiment the 24 conditions of which are described in Example 6.

DETAILED DESCRIPTION OF THE INVENTION
2 in its broadest aspect, the present invention involves improving thermal s oxidative stability of engine oil by using PAO derived from a 1-dodecene or 4 1-tetradecene as a base oil.
The difficulties encountered with the use of PAO based on 1-decene as s feedstock can be avoided by the use instead of PAO 5 and 7 based on 1-dodecene or 1-tetradecene.
a It has also been found that PAO 5/7 offers superior oxidation stability during s use in comparison to PAO 4/6. As the examples below show, such improved 0 oxidation stability is found in both gasoline (T-4) and diesel (TDI) engines ~ (especially direct injection diesels). Furthermore, the superior oxidation ~2 stability qualities are shown in both fully synthetic as well as semi-synthetic 3 engine oils, which are a mixture of PAO's and mineral oils.
14 PAO 5/7 has also been shown to be superior over PAO 4I6I8 in PSA TU3M
~5 high temperature gasoline tests and Sequence IIIE high temperature ~ s oxidation tests.
ADDITIVE COMPONENTS
~s The following additive components are examples of some components that ~s can be favorably employed in the present invention. These examples of 2o additives are provided to illustrate the present invention, but they are not 2~ intended to limit it:
22 (1 ) Metal detergents: sulfurized or unsulfurized alkyl or alkenyl phenates, 23 alkyl or alkenyl aromatic sulfonates, sulfurized or unsulfurized metal 24 salts of multi-hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl or 2 alkenyl naphthenates, metal salts of alkanoic acids, metal salts of an s alkyl or alkenyl multi-acid, metal salts of an alkyl salicylic acid, 4 carboxylates, overbased detergents and chemical and physical mixtures thereof.
s (2) Ashless dispersants: alkenyl succinimides, alkenyl succinimides modified with other organic compounds, and alkenyl succinimides s modified with boric acid, alkenyl succinic ester.
s (3) Oxidation inhibitors:
~o (a) Phenol type oxidation inhibitors: 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methyl-6-~2 tert-butylphenol), 2,2'-(methylenebis (4-methyl-6-tert-butyl-phenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), ~a 4,4'-isopropylidenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), ~s 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl-17 4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butyl-phenol, 2,6-di-tert-4-(N.N' dimethylaminomethylphenol), s 4,4'-thiobis(2-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-2o tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)-2~ sulfide, and bis (3,5-di-tert-butyl-4-hydroxybenzyl).

22 (b) Diphenylamine type oxidation inhibitor: alkylated diphenylamine, 23 phenyl-I-naphthylamine, and alkylated I-naphthylamine.
2a (c) Other types: metal dithiocarbamate (e.g., zinc dithiocarbamate), 25 and methylenebis (dibutyldithiocarbamate).

_g_ ~ (4) Rust inhibitors (Anti-rust agents):
2 (a) Nonionic polyoxyethylene surface active agents: polyoxyethylene s lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene 4 nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene ofeyl ether, s polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol 7 mono-oleate, and polyethylene glycol monooleate.
s (b) Other compounds: stearic acid and other fatty acids, dicarboxilic acids, metal soaps, fatty acid amine salts, metal salts of heavy o sulfonic acid, partial carboxylic acid ester of polyhydric alcohol, and phosphoric ester.
~2 (5) Demulsifiers: addition product of alkylphenol and ethyleneoxide, ~3 polyoxyethylene alkyl ether, and polyoxyethylene sorbitan ester.
14 (6) Extreme pressure agents (EP agents): zinc dithiophosphates, zinc 5 dithiocarbamates, zinc dialkyldithiophosphate (primary alkyl type &
~s secondary alkyl type), zinc diaryl dithiophosphate, sulfurized oils, 17 Biphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, ~s fluoroalkylpolysiloxane, and lead naphthenate.
~s (7) Friction modifiers: fatty alcohol, fatty acid, amine, borated ester, and 20 other esters.
2~ (8) Multifunctional additives: sulfurized oxymolybdenum dithiocarbamate, 22 sulfurized oxymolybdenum organo phosphoro dithioate, 23 oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, 24 amine-molybdenum complex compound, and sulfur-containing 2s molybdenum complex compound.

_g_ (g) Viscosity index improvers: polymethacrylate type polymers, ethylene-2 propylene copolymers, styrene-isoprene copolymers, hydrated styrene-s isoprene copolymers, polyisobutylene, and dispersant type viscosity 4 index improvers.
s (10) Pour point depressants: polymethyl methacrylate.
s {11 ) Foam inhibitors: alkyl methacrylate polymers and dimethyl silicone 7 polymers.
s In one embodiment, an engine lubricating oil composition would contain:
s (a) a major part of a base oil of lubricating viscosity, wherein the base oil comprises 1-dodecene and/or 1-tetradecene-derived polyalphaolefins;
(b) 0% to 20% of at least one ashless dispersant;
~2 {c) 0% to 30% of the detergent;
13 (d) 0% to 5% of at least one zinc dithiophosphate;
14 (e) 0% to 10% of at least one oxidation inhibitor;
(f) 0% to 1 % of at least one foam inhibitor; and ~s {g) 0% to 20% of at least one viscosity index improver.
7 In a further embodiment, an engine lubricating oil composition is produced by 8 blending a mixture of the above components. The lubricating oil composition 19 produced by that method might have a slightly different composition than the 2o initial mixture, because the components may interact. The components can 2~ be blended in any order and can be blended as combinations of components.

ADDITIVE CONCENTRATES
2 Additive concentrates are also included within the scope of this invention.
s The concentrates of this invention comprise the compounds or compound 4 mixtures of the present invention, with at least one of the additives disclosed above. Typically, the concentrates contain sufficient organic diluent to make s them easy to handle during shipping and storage.
7 From 20% to 80% of the concentrate is organic diluent. Suitable organic s diluents which can be used include for example, solvent refined 100N, i.e., s Cit-Con 100N, and hydrotreated 100N, i.e., RLOP 100N, and the like. The 0 organic diluent preferably has a viscosity of from about 1 to about 20 cSt at ~ 100°C.
~ 2 EXAMPLES
~3 The invention will be further illustrated by following examples, which set forth 14 particularly advantageous method embodiments. While the Examples are ~5 provided to illustrate the present invention, they are not intended to limit it.
16 Examples 1 through 4 cover bench test data obtained in the proprietary MAO
~ 92 oxidation bench test. In this test, air is bubbled through an oil,sample at s elevated temperature. The oil sample contains an oxidation catalyst. The 9 viscosity of the oil at 40°C is measured at regular intervals until 1000 cSt is 2o reached. The time to reach this value is a measure of the stability. The 2~ longer the time, the better the oxidation stability. The MAO 92 oxidation test 22 has a repeatability of 7 hours.

2 A fully formulated engine oil was prepared, containing an additive package s comprised of 6% dispersant, 71.5 mmol detergent, 15.5 mmol zinc a dithiophosphate, 0.55% supplementary additives, 2.0% VII, 34.8% Esso s 145N, 20.55% Esso 600N and 15% PAO 5 and 15% PAO 7. This oil was s subjected to the MAO 92 oxidation test, the result being 125 hours.

s As a comparison, a similar engine oil as described in Example 1 was s prepared. However, the 15% PAO 5 and 15% PAO 7 were replaced by 30%
PAO 6. The result of the oxidation test was only 100 hours.

~2 The experiment of Example 1 was repeated using an additive package ~ 3 comprised of 6% dispersant, 71.5 mmol detergent, 15.5 mmol zinc ~a dithiophosphate, 0.55% supplementary additives, 2.0% VII, 52% PAO 5 and ~ s 33.3% PAO 7. The result in the oxidation test is 162 hours.

17 As a comparison to Example 3, the PAO 5 and 7 were replaced by 11.1 ~a PAO 4 and 74.2% PAO 6. The result in the oxidation test, 152 hours, was ~ s poor in comparison to the oil of Example 3.
2o EXAMPLE 5 2~ The oils of Example 1 and Comparative Example 2 were subjected to the 22 bench tests used to mimic the viscosity increase of the VW T-4 engine test.
2s The lower the absolute and relative viscosity increase, the better the test result. As can be seen in Figure 1, the oil based on PAO 517 is far superior to 2 the oil based on PAO 6.

Oil code OIL 10 OIL 11 Additive package AP7 AP7 Calculated T-4 viscosity756.6 201.8 (cSt) Calculated T-4 viscosity819.0 189.7 increase (%) s A fully formulated engine oil was prepared containing an additive package 7 comprised of 6% dispersant, 87 mmol detergent, 19 mmol zinc $ dithiophosphate and 0.35% supplementary additives, 10.3% VII and 30%
s PAO 5, the balance made up by mineral base stock. Two similar engine oils to were prepared but the 30% PAO 5 was replaced by 30% PAO 4 and 30%
~ PAO 6, respectively. These three oils were subjected to the bench tests used ~2 to mimic the viscosity increase of the VW T-4 engine test. The lower the ~3 absolute and relative viscosity increase, the better the test result. As can be ~a seen in Figure 2, the oil based on PAO 5 is far superior to the oils based on ~ 5 PAO 4 and PAO 6.

Oil code OIL 13 OIL 12 OIL 14 Additive package AP4 AP4 AP4 Calculated T-4 99.4 258.2 154.3 viscosity (cSt) Calculated T-4 10.5 212 79.5 viscosity increase (%) a A fully formulated engine oil was prepared containing an additive package s comprised of 6.5% dispersant, 98 mmol detergent, 5.5 mmol zinc s dithiophosphate and 1.8% supplementary additives, 4.0% VI improver and the z balance a 57.6/42.4 mixture of PAO 4 and PAO 6. This oil was run in the VW
s TDI engine. The test was aborted after 52 hours, i.e., 8 hours before s reaching the end-of-test, as result of low oil pressure due to a lack of engine oil remaining in the sump.
A VW TDI test was conducted on a 1.9 liter turbo charged, intercooled DI
~2 diesel type engine. The engine tested has power of 81 kW at 4150 rpm's.
13 There are 4 cylinders in the engine measuring 79.5 x 95.5 mm (b x s). EGR
4 is not activated in the engine and the oil charge is 4.5 liters. The test ~5 procedure had a 5 hour run-in step, a 3 hour power curve step, and a 2 hour s flushing step.
~ These steps were followed by a 60 hour cycling step which had two stages:
~s stage 1, the idling stage; and stage 2, the full load stage. One cycle takes three hours and the cycle was repeated 20 times (20 x 3 hrs.). Further facts 2 about the cycling stage are given in Table 3 below.

a CEC L-78-T-96 (TDI) Engine Test Test Conditions Stage 1 Stage 2 Duration (minutes) 30 150 Speed (rpm) Idle 4150 Oil Temperature (C) 40 145 Coolant Temperature (C) 30 90 Boost Air Temperature 30 60 (C) s 8 As a comparison to Example 6, the PAO 4 and 6 were replaced by 8.6%
9 PAO 5 and 91.4% PAO 7. The oil successfully completed the 60 hour VW
~o TDI engine test.

~2 T-4 bench tests and engine tests were performed on oil compositions ~3 containing various additives, including viscosity index improvers and various ~a proportions of PAO 4, PAO 5, PAO 6, PAO 7, PAO 8 and mineral stock.
15 Tables 4A through 4D show the T-4 bench test and engine test results as well as the MAO 92 results for the compositions. These results show the correlation between the engine test results and the bench test model for both the absolute viscosity at end-of-test (EOT) and also for the relative viscosity ~s increase. Both are requirements for the T-4 test.

1 The Engine Test Conditions for conducting the VW T-4 test are given below in 2 Table 4. The total test had a duration of 262 hours (10 hours run-in, +
3 2 hours power curve, + 2 hours flushing, + 48 x PNK cycles = 48 x 4 = 192 hrs, + 56 hrs N cycle ~ 262 hours). The test oil charge was 5 liters with no oil top-up allowed. Of the various test requirements, the limits on viscosity s increase are the most difficult to achieve. Both relative viscosity increase as 7 well as absolute viscosity increase at EOT are limited. The limits are as s follows: EOT Viscosity at 40°C <200 cSt.
s EOT Viscosity increase <130%.

Oil Code OIL 1 OIL 2 OIL 3 Additive Package AP1 AP 2 AP3 --dispersant (wt%) n.a. 5 6.75 --detergent (mmol) n.a. 84 70 -zinc dithiophosphate (mmol)n.a. 18 18 -supplementary additives n.a. 1.6 0.93 (wt%) VI Improver (%) n.a. 4.7 10.5 Vllmprover polymethyl-ethylene acrylate propylene type copolymers polymers (OCP) (PMA) PAO 4 n.a.

PAO 5 n.a.

PAO 6 n.a. 62.1 25 PAO 7 n.a.

PAO 8 n.a. 20 Mineral Stock (%) n.a. 50.6 Mineral Stock n.a. full Group 1 synth.

TGA (C) 336.8 342.5 312.5 MAO 92-vise. at 100 H (eSt)69.3 125.9 180.1 MAO 92-vise. increase at -9.8 65.9 87.1 (%) Calculated VW T-4 viscosity107.8 114.1 302.8 increase (cSt) Calculated VW T-4 viscosity47.9 55.3 264.0 increase (%) Act. T-4 vise. increase 134.2 107.0 450.9 (cSt) Act. T-4 vise. increase 74.5 41.0 368.5 (%) Oil Code OIL4 OILS OIL6 Additive Package AP2 AP4 AP5 --dispersant (wt%) 5 6 6.5 --detergent (mmol) 84 87 98 -zinc dithiophosphate (mmol)18 19 15.5 -supplementary additives 1.6 0.35 1.8 (wt%) VI Improver (%) 6.2 9 6.3 Vllmprover OCP OCP Styrene isoprene copolymers (Styr.-I
P) PAO 4 45.5 PAO 6 21.8 23.5 13.1 Mineral Stock (%) 58.8 55 20 Mineral Stock Group I Group I Group Il TGA (C) 316.2 318.7 320 MAO 92-visc. at 100 H (cSt)1344.6 190.9 74 MAO 92-visc. increase at 1326.5 108.7 32.3 (%) Calculated VW T-4 viscosity1017.4 277.2 197.3 increase (cSt) Calculated VW T-4 viscosity971.1 236.2 182.7 increase (%) Act. T-4 visc. increase Too viscous335.4 151.7 (cSt) to measure Act. T-4 visc. increase 268.0 171.2 (%) Oil Code OIL7 OIL8 OIL9 Additive Package AP5 AP5 AP6 --dispersant (wt%) 6.5 6.5 6 --detergent (mmol) 98 98 93 -zinc dithiophosphate (mmol)15.5 15.5 19 -supplementary additives 1.8 1.8 1.6 (wt%) VI Improver (%) 5.2 5.0 5.0 Vllmprover Styr.-IP Styr.-IP Styr.-IP

PAO 4 43 15.98 15.98 PAO 5 63.92 63.92 PAO 6 36.7 Mineral Stock (%) Miners! Stock TGA (C) 314 353 355 MAO 92-visc. at 100 H (cSt)53.8 51.1 -25.4 MAO 92-visc. increase at -1.3 50.5 -25.3 (%) Calculated VW T-4 viscosity215.5 12.9 -45.6 increase (cSt) Calculated VW T-4 viscosity202.1 -22.4 -80.2 increase (%) Act. T-4 visc. increase 115.0 (cSt) Act. T-4 visc. increase 108.0 (%) Oil Code OIL10 OIL11 Additive Package AP7 AP7 --dispersant (wt%) 6 6 --detergent (mmol) 71.5 71.5 -zinc dithiophosphate (mmol)15.5 15.5 -supplementary additives 0.55 0.55 (wt%) Vl Improver (%) 2.0 2.0 VI Improver OCP OCP

Mineral Stock (%) 55.3 55.3 Mineral Stock Group I Group I

TGA (C) 310 325 MAO 92-visc. at 100 H (cSt)880 122 MAO 92-visc. increase at 1000 99.7 (%) Calculated VW T-4 viscosity756.6 201.8 increase (cSt) Calculated VW T-4 viscosity819.0 189.7 increase (%) Act. T-4 visc. increase (cSt) Act. T-4 visc. increase (%) VW PV 1449 ENGINE TEST (T-4) Test Conditions PNK Cycles Max Max NOX Cold IdlingMax NOx Power N K N
P

Duration 120 min 72 min 48 min 56 hrs Oil Sump Temp C 133 130 40 130 Coolant Temp C 100 100 30 100 Power kW 62 34 0 34 Torque Nm 140 75 0 75 Fuel Cons. kglh 19.4 10.8 1.1 10.8 .

Exh. Gas Temp C 820 763 292 763 Oil Code Oil 12 Oil 13 Oil 14 --dispersant (wt%) 6 6 6 --detergent (mmol) 87 87 87 -zinc dithiophosphate 19 19 19 (mmol) -supplementary additives0.35 0.35 0.35 (Wt%) VI IMPROVER (%) 10.4 10.3 10.7 VIIMPROVER OCP OCP OCP

MINERAL STOCK (%) 47.1 47.2 46.8 MINERAL STOCK Gr. IIIII Gr. Illll Gr. I/III

4 Bench Test Thermal Gravimetric Analysis (TGA) of PAO 5 and 7 s Bench test analysis was performed on four different samples of oil to find the s TGA DPeak (i.e. the temperature at which the weight loss, due to both z evaporation and oxidation, of the oil is the most important, which correlates s with oil consumption). This test measures the weight variation of a sample as s a function of temperature, under a nitrogen flow. At a certain temperature, ~o defined as the DPeak, the weight loss is the most important. The exact ~ DPeak value is determined as the maximum of the derivative curve. The 2 repeatability of the TGA test is equal to 8°C. Table 7 shows the results.

Test Test 2 Test 3 Test 4 Dispersant wt% 6.5 6.5 6 6 Detergent mmol 98 98 71.5 71.5 Zinc 15.5 15.5 15.5 15.5 dithiophosphate mmol Supplementary 1.8 1.8 0.55 0.55 additives wt%

Vllwt% 5.2 5.2 2.0 2.0 PAO 4/6 wt % 43136.7 PAO 4/5 wt % 15.98/63.92 PAO 6 wt % 30 PAO 5l7 wt % 30 Mineralstock 55.3 Esso 55.3 Esso wt %

TGA (C) 314 353 310 325 s A fully formulated engine oil was prepared, containing 13.6% of an additive 7 package, 6.9% VI Improver, 10% ester and 35% PAO 5 and 34.5% PAO 7. A
s Seq. IIIE test was run on this oil with a 1986 3.8 liter Buick V6 engine using 9 leaded gasoline. The initial oil fill is 5.3 liters. Totaf test duration is 64 hours.
~o The engine speed is 3000 rpm with a load of 50.6 kW. The oil temperature is 11 149°C. The results of the test were as follows:

- viscosity increase: -11 - 2 - time to 375% vis. incr.: 87.3 hours s - Aver. engine sludge: 9.7 4 - oil consumption, titer 0.67 As a comparison, a similar engine oil as described above was prepared.
s However, the 35% PAO 5 and 34.5% PAO 7 were replaced by 69.5% PAO 6.
Again, a Seq. IIIE was run, resulting in:
- viscosity increase: -1 g - time to 375% vis. incr.: 85.8 hours o - Aver. engine sludge: 9.6 11 - oil consumption, liter 1.14 ~2 While the present invention has been described with reference to specific ~3 embodiments, this application is intended to cover those various changes and 4 substitutions that may be made by those skilled in the art without departing ~ 5 from the spirit and scope of the appended claims.

Claims (8)

CLAIMS:

1. The use of PAO derived from alpha olefins consisting essentially of 1-dodecene and having an approximate viscosity at 100°C of from 3.5 to 9.5 centistokes, as the base oil, or a component of the base oil, of an engine oil for the purpose of improving the high temperature stability of the engine oil when compared with the use of a 1-decene derived PAO.

2. The use of PAO derived from alpha olefins consisting essentially of 1-dodecene and having an approximate viscosity at 100°C of from 3.5 to 9.5 centistokes, as the base oil, or a component of the base oil, of an engine oil comprised of base oil, dispersants, detergents, oxidation inhibitors, foam inhibitors, anti-wear agents and at least one viscosity index improver, for the purpose of improving the high temperature stability of the engine oil to least the point at which the engine oil is able to pass the VW
T-4, VW TDI, or sequence IIIE tests.

3. The use according to Claim 1 or 2 wherein the base oil is from 15 to 85% of the engine oil and at least 15% of the base oil is PAO derived from alpha olefins consisting essentially of 1-dodecene.

4. The use according to C 1, 2 or 3 wherein the PAO is from 50 to 85% of the base oil for OW-xx SAE
viscosity grade oils where XX=20-40, is from 15 to 50%
of the base oil for 5W-xx SAE viscosity grade oils where xx=20-50, or is from 5 to 35% of the base oil for 10W-xx SAE viscosity grade oils where xx=20-50.

5. An engine oil having a SAE viscosity grade of OW-xx where xx denotes 20-40 comprised of from 15 to 85% base oil having from 50 to 85% PAO derived from alpha olefins consisting essentially of 1-dodecene and having an approximate viscosity at 100°C of from 3.5 to 9.5 centistokes, from 0 to 20% of at least one ashless dispersant; from 0 to 30% of detergent; from 0 to 5% of at least one anti-wear agent; from 0 to 10% of at least one oxidation inhibitor; from 0 to 1% of at least one foam inhibitor; and from 0 to 20% of at least one viscosity index improver.

6. An engine oil having a SAE viscosity grade of 5W-xx where xx denotes 20-50 comprised of from 15 to 85% base oil having from 15 to 50% PAO derived from alpha olefins consisting essentially of 1-dodecene and having an approximate viscosity at 100°C of from 3.5 to 9.5 centistokes, from 0 to 20% of at least one ashless dispersant; from 0 to 30% of detergent; from 0 to 5% of at least one anti-wear agent; from 0 to 10% of at least one oxidation inhibitor; from 0 to 1% of at least one foam inhibitor; and from 0 to 20% of at least one viscosity index improver.

7. An engine oil having a SAE viscosity grade of 10W-xx where xx denotes 20-50 comprised of from 15 to 85% base oil having from 5 to 35% PAO derived from alpha olefins consisting essentially of 1-dodecene and having an approximate viscosity at 100°C of from 3.5 to 9.5 centistokes, from 0 to 20% of at least one ashless dispersant; from 0 to 30% of detergent; from 0 to 5% of at least one anti-wear agent; from 0 to 10% of at least one oxidation inhibitor; from 0 to 1% of at least one foam inhibitor; and from 0 to 20% of at least one viscosity index improver.

8. The use according to Claim 1, 2, 3 or 4 or the engine oil according to Claim 5, 6 or 7 wherein the PAO has an approximate viscosity at 100°C of approximately 5 centistokes or approximately 7 centistokes.