CA2919739A1

CA2919739A1 - Lubricating oil compositions with enhanced piston cleanliness

Info

Publication number: CA2919739A1
Application number: CA2919739A
Authority: CA
Inventors: Richard Hogendoorn; Bertus Bernardus Hoogendam
Original assignee: Chevron Oronite Technology BV
Current assignee: Chevron Oronite Technology BV
Priority date: 2015-02-13
Filing date: 2016-02-03
Publication date: 2016-08-13
Also published as: EP3056556B1; EP3056556A1; SG10201601063QA; CN105950262B; CN105950262A

Abstract

Disclosed herein are low and medium sulfur, phosphorus, and sulfated ash (low and medium "SAPS") lubricating oil compositions for providing enhanced piston cleanliness in an internal combustion engine. The lubricating oil compositions comprise at least one Mannich reaction product prepared by the condensation of a polyisobutyl-substituted hydroxyaromatic compound, wherein the polyisobutyl group is derived from polyisobutene containing at least 70 wt. % methylvinylidene isomer and has a number average molecular weight of from 400 to 2,500, an aldehyde, an amino acid or ester derivative thereof, and an alkali metal base.

Description

LUBRICATING OIL COMPOSITIONS WITH
ENHANCED PISTON CLEANLINESS
BACKGROUND OF TH INVENTION
I. Technical Field [0001] The present invention generally relates to low and medium sulftir, phosphorus, and sulfated ash (low and medium "SAPS") lubricating oil compositions to enhance piston cleanliness in internal combustion engines.

2. Description of the Related Art [0002] The viscosity grade of an engine oil is a key feature when selecting a lubricating oil. The lubricating oil is typically chosen according to both the climatic temperatures to which the engine is exposed, and the temperatures and shear conditions under which thc engine operates. Thus, the o11 must be of sufficiently low viscosity at ambient temperatures to ploy ide adequate lubrication upon cold starting of the engine, and capable of maintaining sufficient viscosity to lubricate the engine when it is under a full operating load.

[0003] The Society of Automotive Engineers classification system, SAE BOO, defines engine oil giadc viscoily specifications. Single grades are designated as SAE 70, 30, 40, 50, and 60 grade, and are defined by a low shear rate kinematic viscosity range at 100 C
(ASTM D445), as well as a minimum high shear rate viscosity at 150cC (such as ASTM
D4683, CEC L-36-A 90, or ASTM D5481). Engine oils designated as SAE OW through 25W have been classified according to their low temperature cranking viscosities (ASTM
D5293), low temperature pumping viscosities (ASTM4684), and a minimum kinematic viscosity at I00 C.
10004] Multi-grade lubricating oils perfoun over wide temperature ranges.
Typically, they are identified by two numbers such as, for example, 1W-10 or 10W-30 The first number in the mold-grade designation is associated with a sate cranking temperature (e.g,, -20 C) viscosity requirement foi that multi-grade oil as measured by a cold cranking 5irnulator (CCS) under high shear ran (ASTIVI D5293). In general, lubricants that have low CCS
viscosities allow the engine to crank more easily at lower temperatures and thus improve engine startability at thosc ambient temperatures.
[00051 The second number In the multi-grade designation is associated with a lubricant's viscosity under normal operating temperatures and is measured in terms of the kinematic viscosity (Kv) at 100 C (ASTM D445). The high temperature viscosity requirement brack.cts minimum and iiiimitnurn kinematic viscosity at 1004C.
Viscosity at nigh temperatures Is desirable to prevent engine wear that would result if the lubricant thinned out too much during engine operation. However the lubricant should nut be Lou viscous because excessivc viscosity may Cut= unnecessary viscous drag and work to pump the lubricant which in turn can increase fbel consumption, In general, the lower a lubricants' Kv I00 C, the better the scores that lubricant achieves in fuel economy tests.
[0006] Thus, in order to qualify for a given multi-giade oil designation a particular multi-grade oil must simultaneously meet both strict low and high temperature viscosity requirements that are set by SAL: specifications such as SAE J300.
[001)7.1 Merely blending base stocks of different viscosity characteristics may not enable the formulator to meet the low and high temptiature viscusity requirements of some multi-grade oils. The formulator's primary tool for achieving this goal is an additive conventionally referred to as a viscosity modifier or viscosity index (V.I.) improver. Usually, to reach the minimum high temperature viscosity required, it is neccssary La add significant amounts of viscosity modifier. However, the use iyr an increased amount of viscosity modifier results in increased low temperature lubricant viscosity, The ever increasing need to formulate crankcase lubricants that deliver improved perfonnanec in fuel economy tests is driving the industry to engine lubricants in the lower viscosity grades. such as SAE OW-20, 0W-30, 5W-20 and 5W-30.
[00081 Concurrent with the demand for lower viscosity, high fuel economy lubricants, there has been a continued effort to reduce the content of sulfated ash, phosphorus and sulfa' in the crankcase lubricant due to both environmental concerns and to insure compatibility with pollution control devices used in comhination with modern engines (e.g., three-way catalytic converters and particulate traps). A particularly effective class of antioxidant-antiwear additives available to lubricant formulators is metal salts of dialkyldithiophosphates.
Particularly zinc salts thereof, commonly referred to as ZDDP. While such additives provide excellent performance, ZDDP contributes each of sulfated ash, phosphorus and sulfur to luhriCantS.
10009] Catalytic convcrtcrs typically contain one or inure oxidation catalysis, NOT
storage {;i1Lelyt, and/or NH3 reduction catalysts. The catalysts contained therein generally comprise a combination of catalytic, metals such as platinum, and metal oxides. Catalytic Ctinverters are installed in the exhaust systems, for example, thc exhaust pipes of automobiles, to convert the toxic gases to nontoxic gases. The use of catalytic univerter is thought to bc essential in bucking global warming trends and combating other environmental detriments. The catalysts, however, can be poisoned and rendered less effective, if not useless, as a result of exposure to certain cicrnonts or compounds, especially phosphorus compounds such as ZDDP.
100101 Particulate traps are usually installed in the exhaust system, especially in clicsal engines, to prevent the carbon black particles or very fine condensate particles or agglomerates thereof (i.e., "diesel soot") from being released into the environment. Aside from polluting air, water, and other elements of the environment, diesel son' is a recognized carcinogen. These traps, however, can he blocked by metallic ash which is the degradation product of metal-contaiiiiiiR, lubricating oil additives including common ash-producing detergent additives.
[0011] To insure a long service life for the after-treatment devices, it is desirable to identify lubricating oil additives that exert a minimum negative impact on such devices. TO
this end, OEMs often set various limits for maximum sulfiir, phosphorus, ancUor sulfated ash levels for "new service fill" and "first till" lubricants. For example, when used in light-duty passenger-car internal combustion engines, the sulfur levels are typically required to be at or below 0,30 wt. 'Yu, the phosphorus levels at or below 0.08 wt. %, and the sulfated ash content at or below 0,8 wt. %. The maximum sulflir, phosphorus and/or sulfated ash levels may differ, however, when the lubricating compositions arc used in heavy-duty internal combustion engines. For example, the maximum blliked ash level may be as high as L6 wt.
% in those hcavy-duty engines. Such hibricating oil compositions are also referred to as "medium SAPS" (i.e., medium sulfated ash, phosphorus, and sulfur). When the maximum sulfated ash level is as high as 1.0 wt. thc lubricating oil compositions arc referred to as "low SAPS" lubricating oil ccuiipviIiuru, e.g., For gasoline engines, and "LEIDI: (i.e., low emission diesel lubricant) oil compositions tbr diesel engines.
[0012] Various tests have been established and standardized to measure the levels of SAT'S in any particular lubricating ull cumpusiliusis. Fur example, in Europa, a lubricant meeting the ACF.A gasoline and diesel engine low SAPS specification must pass, inter alia, the ''CEC L-1X-1-99" test, which measures the cleanliness and extent of piston ring sticking after running a Volkswagen turbocharged direct injection automotive diesel engine for an extended lime period, cycling alternatively between idle and full power.
Similar spe.Mfications and testing standards of varied stringencies can also be found in other countries and regions, such as Japan, Canada, and the United States.

4 [00131 Meeting the low SAPS environmental standards however does nrn eliminate the need to provide adequate lubricant performance. Automobile spark ignition and diesel engines have valvc, train systems, including valves, Cams, and rocker arms, all of which must be lubricated and protected from wear. Furthel, enine oils must provide sufficient detergency so as to insure engine cleanliness and suppress the production of deposits, which are products of non-combustibles and incomplete, combustibles of hydrocarbon fuels and deterioration of engine oils.
[00141 As discussed above, the need to preserve the Integrity of catalytic converters has led to the use of le.ss phosphate and phosphorus-containing additives.
However, the uso of detergents, which are typically metal sulfonate detergents, is often inevitable because of thc sustained needs to neutralize the oxidation-derived acids and suspend polar oxidation residues in the lubricant These, detergents, however, contribute to the production of sulfated ash. The amount of ash permitted under most of the current environmental standards can be exceeded by far less metal sulfonatc detergent than is necessary to achieve adequate detergency performance. Reducing the levels of detergent overbasing may reduce the level of ash produced, but it also reduces the acid neutralizing capacity of the lubricant composition, potentially leading to acid corrosion of the engine pistons and other parts.
[0015] Oil-so]uble Manilla condensation products are useful in internal combustion engine lubricating ails. These products generally act as dispersants to disperse sludge, varnish, and lacquer, and prevent the formation of deposits. In general, conventional oil-soluble Mannich condensation products ace founed Crum the reaction of polyisobutyl-substituted phenols with formaldehyde and an amine nr s pnlyamine. For example, U.S.
Patent NOS. 7,964,543; 8,394,747; 8,4681; 8,722,927 and 8,729,297 disclose that 0,01 wt.
% to 10.0 wt. % of a Mannich condensation product formed by combining, under reaction condition; a polyisobutyl-substitutcd hydroxyaroinatic compound wherein the polyisobutyl group is derived from polyisobutenc containing at least 50 weight percent methylvinylidene isoinei and having a number average molecular weight in the range of about 400 to about 50011, an aldehyde, an amino acid or ester thereof, and an alkali metal base, can be used in an engine lubricating oil composition. Each of these patents further disclose in the examples that 1 wt. % of the Mannich condensation product was added to a fillly formulated SAE grade 5W-30 baseline oil, SAP, grade 5W-40 baseline oil and a SAE grade 10W-40 baseline oil.
[90161 Thus, there is a need to provide an improved low and medium SAPS
lubricating oil composition which is a SAE OW multi-grade lubricant that can overcome poor fuel economy performance.
SUMMARY 0 V 1 'HE INVENTION
[0017] In accordance with one embodiment of the present invention, there is provided a lubricating oil composition comprising:
10018] (a) greater than 65 wt. %, based on the total weight of the lubricating oil composition, of a base oil component having a kinematic viscosity (1(v) at 100 C of about 3.5 to about 4.5 centistokes (cSt);
100191 (b) about 3.0 wt. % to about 10 wr %, based on the total weight of the lubricating oil composition, of at least one Mannich reaction product prepared by the condensation of a polyisobutyl-substituted hydroxyaromatic compound, wherein the polyisobutyl group is derived from polyisobutene containing at least about 70 wt. %
meihylvinylidene isomer and hac a number average molecular weight of from about 400 to about 2,500, an aldehyde, an amino Reid or ester derivative thereof; and an alkali metal base;
and 100201 (e) at least uric ash less dispersant other than component (h);
100211 wherein the, lubricating oil composition has a sulfur content of less than or equal to about 0.30 wt. %, a phosphorus content of less than or equal to about 0.09 wt. %, and a sulfated ash content of less than or equal to about 1.60 wt. % as determined by ASTM
$74, based on the total weight of the lubricating oil composition; and further wherein the lubricating oil composition is a multi-gradc lubricating oil composition meeting the specifications for SAE J300 revised November 2007 requirements for a OW-X
multi-grade engine oil, wherein X is 20, 30, 40, 50, or 60.
10022] En accordance with a second embodiment of the present invention, there is provided a method for improving the piston cleanliness of an internal combustion engine, the method comprising operating the imam! combustion engine with A lubricating oil composition comprising:
[0023] (a) greater than 65 vvt, 0/0, based on the total weight of the lubricating oil composition, of a baso oil component having a Kv at 100T of about 3,5 to about 4.1 cSt;
100241 (b) about 3,0 wt. % to about 10 wt. %, based on the total weight of the lubricating nil composition, of at least one Mannich reaction product prepared by the condensation of a polyisobutyl-substituted hyclroxyaromatic compound, wherein the polyisobutyl group is derived from polyisobutene containing at least about 70 wt. %
methylvinylidene isomer and has a number average molecular weight in the range of from about 400 to about 2,500, an aldehyde, an amino acid or ester derivative thereof, and an alkali metal base; and [0025] (e) at least one ashless dispersant other than component Os);
[0026] wherein the lubricating oil composition has a sulfur content of less than or equal to about 0.30 wt. V0, phosphorus content of less than um equal Lo about 0.09 wt. A, and a sulfated ash content of less than or equal to about 1.60 wt. % as determined by ASTM D
874, based on the total weight the luhricating oil composition; and further wherein the lubricating oil composition is a multi grade lubricating oil composition meeting the specifications for SAE .1300 revised November 2007 rcquilements for a OW-X
multi-grade engine oil, wherein X is 20, 30, 40, 50, or 60.
[0027] In accordance with a third embodiment of the present invention, there is provided a use of a lubricating oil composition comprising:
[00281 (a) greater than 65 wt. %, based on the total weight of the lubricating oil composition, of a base oil component having Kv at 100 C of about 3.5 to about 4.5 eSt;
100291 (b) about 3.0 wt. % to about 10 wt. %, based on the total weight of the lubricating oil composition, of at least one Mannich reaction product prepared by the condensation of a aolyisobutyl-substitured hydroxyaromatic compound, wherein the pulyisobutyl group is derived from polyisobutene containing at least about 70 wt. 0/u me.thyivinylidene isomer and has a number average molecular weight in the range of flout about 400 to about 2,500, an aldehyde, all amino acid or ester derivative thereof, and an alkali metal base; and [00301 (e) at least one ashless dispersant other than component (b);
[0031] wherein the lubricating oil composition has a sulfur eunieni of less than or equal to about 0.30 wt. %, a phospholusi;unLent of less than or equal to about 0.0,) wt. A, and a sulfated ash content Of less than or equal tn ahnnt 1.al wt. Jo as determined by ASTM D
R74, based on the total weight of the lubricating oil composition; and further wherein the lubricating oil composition is a multi-grade lubricating oil composition meeting the specifications fin SAE J300 revised November 2007 requirements for a OW-X
multi-grade engine oil, wherein "X ig i).0, 30, 40, 50, or 60, for improving the piston cleanliness of an internal combustion engine.

[0032] Among other factors, the present invention is based on the surprising discovery that the present combination of dispersants can provide enhanced piston cleanliness performance required in modern low and medium SAPS lubricants which arc SAE OW
multi-grade lubricants for internal combustion engines. By using the present combination of th8 dispenanls, low and medium SAPS lubricants which are SAF. OW multi-grade lubricants can be prepared which pass a piston cleanliness and ring sticking test thereby resulting in improved hid economy performance. In addition, it is believed that the present uornbination of dispersants can further provide seal compatibility in the modern low and medium SAPS
lubricants which are SAE OW multi-grade lubricants for internal combustion engines DETAILED I2LSCRIPTION OP THE PREPERR.ED EMBODIMENTS
100331 Prior to discussing the invention in further derai1, the following terms will be defined:
[0034] DEFINITIONS
10035] As used herein, thc following terms have the following meanings, rmless exPi CNN' Y stated to the contrary:
[0036] The term "Total Base Number" or "TBN" as used heroin refers to the amount of base equivalent to milligrams of K011 in I grain of sample, Thus, higher TBN numbers reflect more alkaline pioducts, and therefore a greater alkalinity reserve.
The '18N of a sample can ha determined by AYI'M 'lest No, D2896-11 issued May 15, 2011 or any other equivalent procedure.
[0037] The term "metal" means alkali metals, alkaline earth metals, or mixture.s thereof.
1001$1 The term "alkaline earth metal" refers to calcium, barium, magnesium, and strontium.

[0039] The term "alkali metal" rem to lithium, sodium, potassium, rubidium, and cesium.
[0040] The term "sulfated ash content" refers to the amount of mctal-containinA
additives (e.g., calcium) magnesium, molybdenum, zinc, ctc.) in a lubricating oil composition and is typically measured according to ASTIVI D874, which is incorporated herein by reference.
[0041] The term "Mannich condensation product" as used herein rcfers to a mixture of products obtained by the condensation reaction of a polylsohutyl-quktitured hYdroxYai unlink:. compound with an aldehyde and an amino acid RS described herein, to form condensation products having the formulas given below, The formulas given below arc provided only as some examples of the Mannich condensation products bclieved tube of the present inrcntion and arc au intended to exclude other possihle Mannich condensation products that may he formed using the methods described herein.
OH
co2x R, OR
CO2X COiX

LR R
= ":-.;-<" -N,...,--"--N--"-N, ..,,,-;,-- "N.
I W/
L li \
CO ,X

I
/
w L 1 w \
,, ;
1 c02, T co,x Y.] Ili W W [ 1 W
\ -:..,,,....,., .....,,, \
CO IX C 02X T co2x ..

OH OH OH
,..N, 1...i ''''''-:;=."-"" \ \k'N z \ N.N. ....--ICO2X CC:17X T
1,vherein R, RI, X and W arc as dcfined heicin.
[0042] The present Invenrion is directed to a lubricatins oil composition comprising:

100431 (a) greater than 65 wt. %, based on the total weight of the luhric,ating oil composition, of a base oil component having a Kv at i of about 3,5 to about 4.5 cSt;
[0044] (h) about 10 wt. % to about 10 wt. D/0, based On thc total weight of thc lubricating oil composition, of at 'cast one Mannich reaction product prepared by the condensation of a polyisobutyl-substituted hydroxyarorna.tic compound, wherein the polyisobutyl group is derived from polyisobutene containing at least about 70 wt. %
methyivinylidene isomer and has a number average molecular weight in the kluge of from about 400 to about 2,500, an aldehyde, an amino acid or ester derivative thereof, and an alkali metal base; and [0045] (c) at least one ashless dispersant other than component (b);
[0046] wherein the lubricating oil cornpo5itiOn has a sulfur content of less than or equal to about 0,30 wt. %, a phosphorus content of less than or equal to about 0.09 wt. %, and a sulfated ash content of less than or equal to about 1.60 wt. V., based on the total weight of the lubricating oil composition; and further wherein the lubricating oil composition is a multi-grade lubricating oil composition meeting the spcuifiattiuris for SAE J300 revised November 2007 requirements for a OW-X multi-grade engine oil, wherein X is 20, 30, 40, 50, or 60.
[0047] The lubricating oil compositions of the present invention arc more desirable from an environmental standpoint than the conventional internal combustion engine lubricating oils that contain higher phosphorous, sulfur and sulfated ash Contents. The lubricating oil compositions of the present invention also facilitate longer service lives for the catalytic converters and the particulate traps, while providing the desired piston cleanliness, [0048] In general, the level of sulfw in the lubricating oil compositions of the present invention is less than or equal to about 0,30 wt. A, /lased on the total weight of the lubricating oil composition, e.g., a level of sulfur of about 0.01 wt. % to about 0.30 wt, %. In one embodiment, the level of sulfur in the lubricating oil compositions of the present invention is less than or equal to about 0.20 wt. A, based On the total weight of the lubricating oil composition, e.g.. a level of sulfur of about 0,01 wt. % to about 0,20 wt. A. In one emhodiment, the level of sulfur in the lubricating oil compositions of thc piesent invention is less than or equal to about 0.10 wt. %, based OR the total weight of the lubricating oil compositiun, e.g., a level of sulfur of about 0.01 wt. % to about 0,10 wt. %, [0049) In one embodiment, the levels of phosphorus in the . lubricating oil compositions of the present invention is less than or equal to about 0.09 wt.
A, based OR the total weight of thc lubricating oil compoNitiun, e.g., a level of phrtsphnnis of about 0.01 wt, %
to about 0,09 wt, %. En one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.08 wt.
%, based un the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. %
to about 0.08 wt. %. hi une embodiment, the levels of phosphorus in the lubricating oil compositions of the. present invention is less than or equal to about 0.07 wt.
%, band on the total weight of the lubricating oil composition, e,g., a level of pliosphurus urabuuL 0.01 wt. 'A
to about 0.07 wt. %. hi one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.05 wt.
9D,13a.se1 on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0,01 wt. %
to about 0.05 wt, %, [0050] In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.60 wt.
% as determined by ASTM D 8711, e.g., a level of sulfated ash of fromn about 0.10 to about 1.60 wt. % as determined by ASTM D 874, In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.00 wt. %
as determined by ASTM D 274, e.g., a level of sulfated ash of from about 0.10 to about 1.00 wt. % as determined by ASTM D 874, In one embodiment, the level of sulfated ash . _ produced by the lubricating oil compositions Of the present invention is less than or equal to about 0,80 wt. 'A as determined by AS FM L) 874, e.g., a level of sulfated ash of from about 0.10 tn about 0.80 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 0.60 wt. % as determined hy ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 0.60 wt. % as determined by ASTM D 874.
[11051] The lubricating oil composition of the present invention Is a fully formulated, low or medium SAPS multi-grade lubrIcatInE nil composition meeting the specifications for SAE 1300 revised November 2007 requirements for OW-X multi grade engine oils, wherein X is 20, 30, 40, 50, or 60. In one embodiment, the lubricating oil composition of the present invention is a fully formulated, low 01 medium SAPS SAE OW-20 multi-grade lubricating oil composition. In one embodiment, tha hihricating oil composition of the present invention is a fully formulated, low or medium SAPS SAE OW-30 multi-grade lubricating oil composition.
In one embodiment, the lubricating oil composition of the present invention Is a filly formulated, low or medium SAPS SAE OW-40 multi-grade lubricating oil composition. In one embodiment, the lubricating oil composition of the present invention is a fully formulated, low or medium SAPS SAE 0W-50 multi-grade lubricating oil euniposition. In one embodiment, the lubricating oil composition of the present invention is a fully formulated, low or medium SAPS SAL OW-60 multi-grade lubricating oil composition.
[0052] ease Oil Component 100531 The lubricating oil composition of the present invention contains greater than 65 wt. it, based on the total weight of the lubricating oil composition, of a base oil component having a Xv at 1009 of about 3.5 to about 4.5 cSt, In practice, this means that the base oil component is selected from one or more natural oils, synthetic oils or mixtures thercof which meet the foregoing Kv requirements at 100 C. In one embodiment, the lubricating Oil composition of the present invention contains at least about 70 wt. %, based on the total weight of the lubricating vil composition, of a base nil component having a Kv at 100 C of about 3.5 to about 4.5 cst in one embodiment, the lubricating oil composition or the present invention contains at least about 75 wt, %, based on the total weight of the lubricating oil composition, of a base oil component having a Kv at 100 C of about 3.5 to about 4.5 eSt.
100541 In one embodiment, the lubricating oil composition of the present invention contains greater than 65 wt. % and up to about 85 wt, based on the total weight of the composition, of a base oil component having a Kv at 100 C of about 3.5 to about 4.5 cSr. In one embodiment, the lubricating oil composition of the present invention contains from about 70 wt. % to about 8 wt. %, based on the total weight of the lubricating oil composition, of a base oil component having a Kv at 100 C of about 3.5 to about 4.5 cSt. In one en ibodiment, the lubricating oil composition of the Few it invention contains from about 75 wt. % to allow 85 wt. %, based on the total weight of the lubricating nil composition, of a base oil component having a Kv at I (10C ot about 3.5 to about 4,5 cSt, .
[0055] In general, the base oil component having a Kv at 100 C of about 3.5 to about 4,5 cSt includes at least one mineral oil basestock. In general, the at least one mineral oil basestook used in the base nil composition is selected from any of the natural mineral oils of API Clumps I ll In, Iv, V or mixtures of these used in crankcase lubricating oils for spark-ignited and compression-ignited engines. API guidelines define a base stock as a lubricant component that may bc manufactured using a variety of different processes.
[00561 Group I base oils generally refer to a petroleum derived lubricating base oil having a saturates content of less than 90 wt. % (as determined by ASTM ID
2007) and/or a total sulfur content of greater than 300 ppm as determined by ASTM D 2622, ASTM D

4294, ASTM 0 4297 or ASTM D 3120) and has a viscosity index (VI) of' greater than or equal to 80 aud JON Wan 120 (as determined by ASTM D 2770) [0057] Group H base oils generally refer to a petroleum derived lubricating base oil having a total sulfur content equal to or less than 300 parts per million (ppm) (as determined by ASTM D 2622, ASTM D 4294, ASTM D 4927 or ASTM D 3120), a saturates content equal to or greater than 90 weight percent (as determined by ASTM 0 2007), and a viscosity index (VI) of between 80 and 120 (as determined by ASTM D 2270), [0058] Group III base oils generally refer to a petioleurn derived lubricating base nil liaviii JGtib than 300 ppm SOW% a saturates content greater than 90 weight percent, and a VI
of 120 or greater. in one embodiment, the Group III base stock contains at least about 95%
by weight saturated hydrocarbons, In another embodiment, the Group III base stuck contains at least about 99% by weight saturated hydrocarbons. The term "major amount"
as IISffi herein Ran amount of greater than SO wt. %, or greater than about 70 wt. %, or from about 80 to about 95 wt. % or from about 85 to about 95 wt, %, based on the total weight of the composition.
[0059] Group TV base oils are: polya iphaipletins (PA0s).
1.00601 Group V base oils include all other base oils not included in Group 1, II, Ill, or IV.
[0061] In one preened embodiment, the base oil component having a Kv at 100 C of about 1.s to about 4.5 cSt is a Group II or Ill basestock. In another preferred embodiment, the base oil component having a Kv at 100 C of about 3.5 to about 4.5 61 is a Group III
basestock.
[0062] The lubricating oil composition can contain minor mounts of other base oil components. For example, the lubricating oil composition can contain a minor amount of a base oil derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof.

Suitable base oil includes base stocks obtained hy isomerization of synthetic wax and slack wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
[0063] Suitable natural oils include mineral lubricating oils such as, for example.
liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the parattinic, naphthenie or tr ixed paraffinic:-naphthenie types, oils derived from coal or shale, animal oils, vegetable oils (e.g., iapeseed oils, castor oils and lard and the like.
11111641 suitable synthetic lubricating oils include, but are not limited to, hydrocarbon oils and halo substituted hydrocarbon oils such as polymerized and interpolymerized olefins, e.g., polybutylones, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hoxenes), poly(I-octenes), poly(1-decenes), and the like and mixtures thereof; alkylbenzencs such as dodecylbenzenes, tctradecylbenzenes, dinonylbenzenes, ni(2-ethylhexy1)-bcnzencs, and th like; polyphenyls such as biphenyls, ter-phenyls, alkylated pulyphcnyls, and the like; alkylated diphcnyl ethers and alkylalcd diptienyl bulfides and Me derivative, analogs and homologs thereof and the like.
[0065] Other synthetic lubricating oils include, but are not limited to, oils made by polymerizing olefins of loss than 5 carbon atoms such as ethylene, propylenc, butylcncs, isohntene, pentene, ancl mho-tires thereof Methods of preparing such polymer rills are well known to those skilled in the art.
[0066] Additional synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful synthetic hydrocarbon oils arc the hydrogenated liquid oligomers of C6 to C. alpha olefins such as, for example, 1.decene trimer.
100671 Another class of synthetic, lubricating oils include, but aie not liinitcd to, alkylene oxide polymers, i.e., homnpolymers, interpolymers, and derivatives thereof where thc terminal hydroxyl groups have been modified by, tor example, esterification or These oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and phenyl ethers uf these polyoxyalkylenc, polymers (e.g., methyl poly propylene glycol ether having An average molecular weight of 1,000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1,000-1,500, ate.) or mono- and polycarboxylic esters thereof such AA, for example, the acetic esters, mixed CI-C* faily acid esters, or the C13 oxo acid diester of tetraethylene 100681 Yet another class of synthetic lubricating oils include, but are not limited to, the esters uf clicarbuxylic acids e.g., plithalic acid, SUccinic acid, alkyl succinic acids, alkenyl suceinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linolcic acid dimer, malonic acids, alkyl malonic acids, alkenyl malonic acids, etc., with a variety of alcohols, r,g,, butyl alcohol, lic-xyl alcohol, dodecyl alcohol, 2-cthylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc. Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)gebacate, di-n-hexyl fumarate, dioctyl scbacatc, diisooctyl azelate, diisodecyl azclate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the alliipieX CSter formed by reacting one mole of sebaeic acid with two rriole.s of tetraethy lane glycol and two moles of 2-cthylhcxanoic acid and the like, 10069] tsters useful as synthetic Oils also include, but are not limited to, those made from carboxylic acids having from about 510 about 12 carbvu atoms with alcohols, e.g., methanol, ethanol, etc., polyols and polyol ethers such as neopentyl glycol, trimethylnI
propane, oentaerythritol, dipcntaerythritol, tripcntacrythritol, and the like.
10070] Silicon-based oils such as, for example, pulyalkyl-, polyaryl-, polyalkoxy- or poiyAryloxy-silmane oils and silicate OilA, comprise another useful class of synthetic lubricating oils. Specific examples of these include, but are not limited to, tetraethyl silicate, tetra-isopropyl silicate, tetra-(2-crhylhexyl) silicate, tetra-(4-methyl hexyl)silicate, tetra-(p-tert-butylphenyl)silicate. hexyl-(41-methy1-2-pentoxy)disiloy,anc, poly(methypsiloxanes, poly(methylphenyl)siloxanes, and the like. Still yet other useful Aynthetic lubricating oils include, but are not limited to, liquid esters of phosphorous containing acids, e.g., tricresyl phosphate, triuctyl phosphate, diethyl ester of &cane phosphionic acid, etc.;
polymeric tetrahydrnfurans and the like.
[0011] The lubricating oil may be derived from unrefined, refined and rerefined oils, either natural, synthetic or mixtures of two or more of any of these of the type disclosed hereinabove. Unrefined oils are those obtained dirn;tly limn a natural or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment. Examples of unrefined ila include, but are not limited to, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or an ester oil obtained directly from an esterification process, each of which is then used without further ircatmerit. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. These purification techniques are known to those of skill in the art and include. for example, solvent extractions, secondary distillation, acid or base extraction, filtration, perenisitinn, hydrntreating, riewaxing, etc.
R.erefined oils are obtained by treating used oils in processes similar to those used to obtain refined oils. Such rerefined oils arc also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
[0072] Lubricating oil base stocks derived from the hydroisomcrization of wax may also be used, eithei alone oi in combination with the aforesaid natural and/or synthetic base ¨

stocks Such wax isomentle vu l is produced by thc hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomcrizaliun catalyst.
100731 Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced hy the Fischer-Tropsch 100711 Mannich Reaction Product [00751 The lubricating oil composition of the present invention will further contain about 3.0 wt.% tu about l 0 wt.%, based on the total weight of the lubricating oil composition, ot at least one Mannich reaction product prepared by the condensation of a polyisobutyl-substituted hydroxyaromatic compound, wherein the polyisobutyl group is &rived from pu y i so butenc containing at least about 70 wt i 94 methylvinylidene isomer and has a number average molecular weight in the range of from about 400 to about 2,500, ,an aldehyde, an ammo acid or ester derivative thereof, and an alkali metal base, In gcncral, the principal Mannich condensation product can be represented by the structure of formula I:
OH

Ri wherein each R is independently R' is a branched or linear alkyl having one carbon atom to about 10 carbon atoms, a cycloalkyl having 'loin about 1 carbon atoms to about 10 carbon atoms, an aryl having from about 6 carbon atoms to about 10 carbon atoms, an alkaryl having from about 7 carbon atoms to about 20 carbon atoms, or aralkyl having from about 7 '2.0 =

carbon atoms to about 20 carbon atoms, R1 is a polyisobutyl group derived from polyisobutene containing at lenct about 70 wt. Vo inethylvinylidcno isomer and having a number avcrage molecular weight in the range of about 400 to about 2,500;
[0076] X is hythogen, an alkali motal ion or alkyl having one to about 6 carbon atoms;
100771 W is ¨ICH.1421-, wherein each R¨ is independently IL alkyl having one carbon atom to about 15 carbon atoms, or a substituted-alkyl having one carbon atom to about 10 carbon atoms aud one or more substitucnts selected from the group consisting of amino, amido, benzyl, carboxyl, hydroxyl, hydroxyphenyl, irnidazolyi, imino, phenyl, sulfide, or thiol; and m is an integer trom Ito 4;
100781 Y s hydrogen, alkyl having one carbon atom to about 10 carbon atoms, wherein K' is as defined above, or Yc -,,..
\A/

[0079] wherein Y is -CIIR'01-1, wherein R.' is as defined above; and R, X, and W are as defined above;
[0080] Z is hydroxyl, a hydroxyphenyl group fthe formula:
OH
[0081] Or OH
TW-N-/
\

RI
10082] wherein R, RI, Y', X, and W are as defined ahnve, [0083] and n is an integer from 0 to 20, with the proviso that when n = 0, Z must be:

,Y1 ..,' ....\.. .,.. W
\

RI
[0084] wherein K, R1, Y', X, and W are as defined above, [n fift.i] In me ernhoriimenr, The RI polylsohutyl group has a number average molecular weight of about 500 to about 2,500, in one embodiment, the R1 polyisobutyl group has a number average molecular weight of about 700 to about 1,500. In one embodiment, the Ri polyisobutyl group has a number average molecular weight of about 700 to about 1,100.
In one embodiment, the R1 polyisobutyl group is derived from polyisohntene cnntaining at least about 70 wt. % mcthylvinylidenc isomer. In one embodiment, the RI
polyisobutyl gioup is derived from polyisobutenc containing at least about 90 wt. 'Yu methylvinylidcne isomer.
100861 In the compound of formula I above, X is an alkali metal ion and most preferably a sodium or potassium ion. In another embodiment, in the compound of formula I
above, X is alkyl selected from methyl or ethyl.

-[0087] In one embodiment, R is CI-12, RI is derived from polyisobutene containing at least about 70 wt. % methylvinylidcric isomer and a number average molecular weight in the iangc of about 700 to about 1,100. W is CH2. X is sodium ion and n is 0 to 20.
[00881 The Mannich condensation products for use in the lubricating oil composition of the present invention can be prepared by combining under reaction conditions a polyisobutyl-substitutcd hydroxyai-omatic compound, wherein the polyisobutyl group has a number average molecular weight in the range of from about 400 to about 2,500, an aldehyde, an amino acid or cstcr derivative thereof; and an alkali metal base.
in one embodiment, Mannich condensation product prepared by the Mannich condensation oh [0089] (a) a poly i subuty I-substituted hydruxyaruniatic. t:om pound having the formula:

_______________________________ R3 Ri wherein 111 is a polyisobuly1 group derived from polyisobutene containing at least about 70 wt. % methylvinylidene isomer and having a number average molecular weight In the range of about 400 to about 2,500, R2 is hydrogen or lower alkyl having one carbon atom to about calbou atoms, and RI is hydrogen or -OH;
[00901 (b) a formaldehyde or an aldehyde having the furrnulai wherein R' is branched or lincar alkyl having one carbon atom to about 10 carbon atom5, oycloalkyl having Iruiri about 3 oarbun alums to about 10 carbon atoms, aryl having from about 6 carbon atoms to about 10 carbon atoms, alkaryl having from about 7 carbon atoms to about 20 carbon atoms, or aralkyl having from about 7 carbon atoms to about 20 carbon alum;
[00911 (c) an amino acid or ester derivative thereof having the formula:

wherein W is -[CHR"]- õ, wherein each R" Is independently 1-1, alkyl having one carbon atom to about 15 carbon atoms, or a substituted-alkyl having one carbon atom to about 10 carbon atoms arid one or more substituents selected from thc group consisting of amino, amido, benzyl, carboxyl, hydroxyl, hydmxyphenyl, imidazulyl, Iminu, phenyl, sulfide, 01 thiol; and m is an integer from one to 4, and A is hydrogen or alkyl having one o.arhon Atom to about 6 carbon atoms; and [0092] (ii) an alkali nicl-al bas.
K16931 Po lv i %oh itvl -cu hxtitute.d Hyri roxyarom all c Compound [0094] A variety of polyisobutyl-substituted hydroxyarornatic compounds can be utilized in the preparation of the Mannich condensation products of this invention. Thc critical feature Is that the polylsobutyl substituent be large enough to impart oil solubility Lu the finished Mannich condensation product. in general, the number of carbon arnm.q on the polyisobutyl substituent group that are required to allow for oil solubility of the Mannich c;uildensation pioduct is on the older of about C20 and higher, This corresponds to a molecular weight in the ranee of about 400 to about 2,500. It Is desirable that the C20 or higher alkyl substituent on the phenol ring he located in the position para to the 014 group on thc phenol.

100951 The polyisobutyl-substituted hydroxyaromatic compound is typically a polyisobutyl-substituted phenol wherein the polyisobutyl moiety is derived from polyisobutene containing at least about 70 wt. methylvinylidene isomer and more preferably the polyisobutyl moiety is derived from polyisobutene containing at least about 90 wt, methylvinylidene isomer. The term "polyisobutyl or polyisobutyl substituent" as used herein refers to the polyisobutyl substituent on the hydroxyaromatic ring, The polyisobutyl substituent has a number average molecular weight in the range uf about 400 to about 2,500.
In one embodiment, the polyisobutyl moiety has a number average molecular weight in the range of about 450 to about 2,500. In one embodiment, the polyisobutyl moiety has a number average molecular weight in the range of about 700 to about 1,500. In one embodiment, the polyisobutyl moiety has a number average mi ecular weight In the range of about '700 to about 1,100.
[009151 In One preferred embodiment, the attachment of the polyisobutyl substituent to the hydroxyaromatic ring is part to the hydroxyl moiety io at least about 60 percent of thc total polyisobutyl-substituted phenol molecules. In one embodiment, the attachment of the polyisobuty1substituent to the hydroxyaromatie ring is para to the hydroxyl moiety in at least about 80 percent of the total polyisobutyl-suk¨tituled phenol molecules. In one embodiment, the attachment of the polyisobutyl substituent to the hydroxyaromatle ring Is para to the hydroxyl moiety on the phenol ring in at least about 90 percent of the total polyisobutyl-substituted phenol molecules.
100971 Di-substituted phenols are also suitable starting materials fur the Mannich condensation products of this invention. Di-substituted phenols are suitable provided that they are substituted in 5uoli a way that there is an unsubstituted ortho position on the phenol ling,. Examples of suitable di-substituted phenols arc o-cresol derivatives substituted in the para position with a C20 or greater polyisobutyl substituent and the like.

[0098] In one emhorlimenr, a polyisohlityl-siihstituterl phenol has the following formula:

whcrcin R1 is polyisobutyl group dcrivcd from polyisobutcnc containing at least about 70 wt.
% methylvinylidene isomer and having a number average molecular weight in the range or about 400 to about 2,500, and Y is hydrogen, [00991 Suitable polyisobutencs may bc prepared using boron tri]uoride (BF3) alkylation catalyst as described in U.S. Patent Nos. 4,152,499 and 4,605,808, the contents of each of these references being incorporated herein by reference. Commercially Available polyisobutenes having a high alkylvinylidene content include Glissopal 1000, 1300 and 2300, a-vailable fiom BASF.
[00100] The preferred polyisobutyl-substituted phenol for use in the preparation of the Mannich condensation products is a mono-substituted phenol, wherein the polyisobutyl substitucnt Ls attached at the porn-position to the phenol ring. However, other polyisobutyl-substitutal phcnols ihai may undcrgo thc Iviannich condensation ruat;tion [nay also be used for preparation of the Mannich condensation products according to the present invention.
[00101] Solvent [00102] Solvents may be employed tu fauililatu handling and reaction of the polyiohnryl-suhstinned phenols in the preparation of the Mannich condensation products.
Examples of suitable solvents are hydrocarbon compounds such as heptane, benzene, toluene, chlorobenzene, aromatic solvent, neutral oil of lubricating viscosity, paraffins and naphthenes. Examples of other commercially available suitable solvents that are aromatic iiiituica include Clinton Ai uniatit; 100N, neuti al oil, Exxon 150N, neutral oil.
[noin3i In one embodiment, the Mannich condensation product may he first dissolved in an alkyl-substituted aromatic solvent. Generally, the alkyl substituent on the aromatic solvent has from about 3 carbon atoms to about 15 carbon atoms. In one embodiment, the alkyl substituent on the aromatic solvent has from about 6 earbon MUM to about 12 unbolt atoms.
[00104) Aldehydes [00105] Suitable aldehydes for use in forming the Hartnich condensation product include formaldehyde or aldehydes having the formula R"I-1 wherein R' is branched or linear alkyl having from one carbon atom to about 10 carbon atoms, oycloalkyl having from about I earhon atoms to about 10 carbon atoms, aryl having from about 6 carbon atoms to about 10 carbon atoms, alkaryl having from about 7 carbon atoms to about 20 carbon atoms, or aralkyl having from about 7 carbon atoms to about 20 c;Eu-bun alums.
[00106] Representative aldehydes include, hut are nor limited to, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraIdehyde, valeraldehyde, caproaldchydc and heptaldchyde. Aromatic aldehydes arc also contemplated for use in the preparation of the Mannich condensation products, such as beimaldellydc and alk.ylbenzaldehyde, e.g., para-tolualdehycle. Also useful are formaldehyde producing reagents, suoh as paraformaldehyde and aqueous formaldehyde solutions such as tortnalin. In one preferred embodiment, an aldehyde for use in the in the preparation of the Mannich condensation products is formaldehyde or formalim 13y formaldehyde is meant all its forms, including gaseous, liquid and solid. Examples of gaseous formaldehyde is the monomer Clip and the trimer, (CI-120)3(trioxane) having the formula given below.
c't Cu( [0(11071 Examples of liquid formaldehyde are the following:
[00108] Monomer C1-120 in ethyl ether.
1001091 Monomer C1120 in water which has thc formulas C1-12(H20)2 (methylene glycol) and F10(-C1-170),-H.
[001101 Monomer CH20 in methanol which has the formulas OHCF120C1-13 and CI430(-C1-120),-1-1.
[001111 Fointaldellycle solutions ale commercially available in water and various alcohols. In water it is availahle as a 17% = :10% solution. Fommlin is a 37%
solution in water. Formaldehyde is also commercially available as linear and cyclic (trioxane) polymers. Linear polymers may be low molecular weight or high molecular weight polyineis.
[00112] Amino Acid [00113] Suitable amino acids or ester derivatives thereof for use in forming the Mannich condensation product include amino acids having thc formula wherein W is ¨[(..:1-11(") õ,-, wherein each R.- is independently H, alkyl having one carbon atom to about 15 carbon atoms, or a substituted-alkyl having one carbon atom to about JO
carbon atoms and one or more substituents selected from the group consisting of amino, amido, benzyl, carboxyl, hydroxyl, hydroxyphenyl, imidzo1yl, imino, phenyl, sulfide, or thiol; and m is an integer from one to 4, and A is hydrogen or alkyl having one carbon atom to about 6 carbon atoms. Preferably thc alkyl is methyl or ethyl.
[001141 In one embodiment, the amino acid Is glycine.
1001151 The term "amino acid salt" as used herein refers to salts of amino acids having the formula VV
cO2M
wherein W is as defined above and M is an alkali metal ion. Preferably M is A
c!)(11iim Ion or a potassium ion. More preferably X is a sodium ion, [001161 Some examples of alpha amino acids contemplated fol use in the preparation of the Man n ich condensation product are given below In Table!.

TABLE I
Log K.25C. 0 ;unit, hticuoli Natne Formula Marline 11"' 9.87 ibc Ci u.
_ _ _ Arginine 8.99 OH

I
MI I, Asparagine I 832 *

111.1, Aspartic Acid 10.0 hLI ' OH
[I' n=
11,2 Cysteine 10.71 ¨C
1=0 - ____________________________ =_ ___________________ Cystine r I
8.80 **
0=0 OH 01.4 Cinnamic Acid 9.95 .2 G1utamine9.01 II I
H3 r C=0 rIt4 9.78 Glycinc I n on Histidine 9.08 =6 G
Hydroxylysine h .3 1-1,131C=C
OTT;
;O.
= _________________________________________________ NHz 1soleueine 9.7) ---C
&13 Cr=0 UM
Leticine 9.75 H, H,C---CH--C---CH
nH
Lysinc NH, 10.69 Fit Hi 14, I
M ethio nine .41.1õ
H, H, 0=0 Phenylulaninc 1 9.31 6-$
NII
Serina 9.21 h, (1111 OH
Thrennine n .õ. r 9.10 pw r==n NN
Tyrosine 10.47 ineNH 9.72 11,C¨r¨r C=-0 0.1 ionic strength.
" 20 C and 0.1 ionic strength.
1001171 Alkali Metal Base [00118] Suitable alkali metal base for use in forming the Mannich condensation product include alkali metal hydroxides, alkali metal alkoxides arid the like.
In one embodiment, the alkali metal base is an alkali metal hydroxide selected from the group consisting of sodium hydroxide, lithium hydroxide or potassium hydroxide.
[00119] In one embodiment, the amino acid may be added in the form of its alkali metal ion tall. In one embodiment, the alkali metal ion is a sodium ion or a potassium ion.
In one preferred embodiment, the alkIi metal ion is a sodium ion.
[00120] General Procedure fur Preparation of Mannich Condensation Product 100121] The reaction to form the Mannich condensation products can he carried out batch wise, or in continuous or semi continuous mode. Normally the pressure for this reaction is atmospheric, but the reaction may be carried out under sub atmospheric or super atmospheric pressure if desired.
[001221 The temperature for this reaction may vary widely. The temperature range for this reaction can vary from about 10 C to about 200 C, or from about 50 C to about 150 C, or fain' aboui 70^C iu about 130C.
[09123] The reaction may be carried out In the presence of a diluent or a mixture of diluents. lt is important to ensure that the reactants come into intimate contact with each other in order for them to react. This is an important consideration because the starting matelials for thc.= lvlanilich condensation products include the relatively non polar polyisohutyl-suhstituted hydroxyl aromatic compounds and the relatively polar amino acid or ester derivative thereof, It is therefore necessary to find a suitable set of reaction conditions or diluents that will dissolve all the starting materials, 1001241 Diluents for this reaction must be capable of dissolving the starting materials of this reaction and allowing the reacting materials to come in contact with each other.
Mixtures of diluents can bc used for this reaction. Useful diluents for this reaction include water, alcohols, (including methanol, ethanol, isopropanol, 1-propanol, 1-butanol, isobulanol, sec-butanol, butanediol, 2-ethylhexanol, 1-pentanol, 1-hexanol, ethylene glycol, and the, like), DMSO, NMP, HMPA, cellosolve, diglyme, various ethers (including diethyl ether, THF, dipncnylether, dioxanc, and the like), aromatic diluents (including toluerie, bonzoic, ci-xylene, m-xylene, p-xylene, mesitylene and the like), e.sters, alkanes (includiq pentane, hexane, heptane, octane,' and the like), and various natural and synthetic diluent oils (including 100 neutral oils, 150 neutral oils, polyalphaolefins, Fischer-Tropsch derived base oil and the like, and mixtures of these diluents. Mixtures of diluents that form two phases such as methanol and heptane are suitable diluents for this reaction.
[00125I The reaction may be carried out by first reacting the hydroxyaromatic compound with the alkali metal base, followed by the addition of the amino acid or ester derivative, thereof And the aldehyde, or the. am r inn acid or ester derivative thereof may he reacted with the aldehyde followed by the addition of the hydroxyaromatic compound and the Alkali metal base, etc,.
[001261 It is believed that the reaction of the amino acid. such as glycine, or ester derivative thereof, plus the aldehyde, such as formaldehyde, may produce the intermediate formula .NH ,cooti 4.
H2N N'COOH fr OH
.000H
.,--[00127] which may ultimately form the cyclic formula COOH
coon -1,4 -N.
L.NCOOH
[OM 281 It iq Mimic] that these intermediates may react with the hydroxyaromatic compound and the base to form the Mannich condensation products of the present invention.
[001291 Alternatively, it is believed that thc reaction of the hydroxyaromatic compound with thc aldehyde may produce the iniermediate formula OH
"OH

[001301 It is also believed that this intermediate may react with the amino acid or ester derivative thereof and the base to form the Mannieh condensation product of the present invention.
it1111311 The time of the reaction can vary widely depending on the temperature. The reaction time can vary between about 0,1 hour to about 20 hours, or from about 2 hours to utioul 10 hours, or from about 3 hours to about 7 hours, [00132] The charge mole ratio (CMR) of the reagents can also vary over a wide range, Table I below gives a listing of the different formulae that can arise if different charge mole ratios are used. At a minimum the oil-solublc Mannich condensation products should preferable contain at least one polyisobutyl-substituted phenyl ring and one amino acid group connected by one aldehyde group and one alkali metal. The polyisohutyl-substituted phenol/aldehyde/amino acid/base charge mole ratio for this molecule, also shown in Table 11 below, is 1.0:1.0: 1.0:1Ø Other charge mole ratios are possible and the use of other charge mole ratios can lead to the production of different Molecules of different formulas.

Product Polyisohntyl=sithstituted phenol : aldehyde :
amino acid : base (CM1() .._ .
.{.)., 1 ( \co1.1 1.0 : 1.0 : 1.0 : 10 I"
1.0:2.0:2.0:2.0 , II I
"CON o Y , 'CILy+i R
,-OH
;=N i's, ..", s.-.),, 2.0 : 2.0 : 1.0 : 1.0 Lj . ..
r ,r 2.0 : 3.0 : 2.0 : 2:0 ( '3 < 'r) rm ,,,ri - T I
3.0 : 4,0 : 2.0 : 2.0 r: T-- ) TI, [00133] Ashless Dispersant 100134.1 '1'he lubricating oil composition of the present invention will further contain at least one ashless dispersant other than the Mannich reaction product discussed hereinabove.
In general, a suitable ashless dispersant can be polyalkylent succinic anhydride ashlcss dispersants, non-nitrogen containing ashless dispersants and basic nitrogen-containing ashless dispersants. One other such group suitable for use herein as a dispersing agent includes copolymers which contain a carboxylate ester with onc or more additional polar function, including amine, amide, lake, lmicle, hydroxyl, carboxyl, and the like. These products can be prepared by copolymerization of long chain alkyl acrylates or methacrylates with monomers of the above function. Such groups include alkyl methacrylate-vinyl pyrrolidinone copolymers. alkyl methacrylate-dialkylarninucthylmelhaurylalc uopulyiners and the like as well as high molecular weight amides and polyamides or esters and polyesters such as tetraethylene pentamine, polyvinyl polystearates and other polystearamides.
1001351 The polyalkylenc succinie anhydride ashless dispersants include polyisohlimnyi succInIc anhydrides (PIRSA). The number average molecular wcighi, of the polyalkylene tail in the polyalkylene succinic anhydrides used herein will be at least about - 350 or from about 750 to about 3000 or from about 900 to about 1100.
[00136J In one embodiment, a mixture of polyalkylene succinic anhydrides is employed. In this embodiment, the mixture nan enmpric . a low molecular weight polyalkylene succinic anhydride component e.g., a polyalkylene succinic anhydride having a number avcragc molecular weight of from about 350 to about 1000, and a high molecular weight polyalkylene succinic anhydride component, e.g., a polyalkylene succinic anhydride having a number average molecular weight of from about 1000 to about 3000. In one embodiment, both the low and high molecular wcight components arc polyisobutcnyl sm.:cline anhydrides. Alternatively, various molecular weights polyalkyletie succinic , , , anhydride components can be combined as a dispersant as well as a mixture of the other above referenced dispersants as identified above, 1001371 Li general, the polyalkylene succinic anhydride is obtained from a reaction prnduct of a pnlyalkylene such as polyisobutene with maleic anhydride.. One can use conventional polyisobutenc, or high methylvinylidene polyisobutcne in the preparation of such polyalkylene succinic anhydrides. The polyalkylene succinic anhydrides can be prepared using conventional techniques e.g., thermal, chlorination, free radical, acid catalyzed, or any other process in this preparation that is within the purview of one skilled in the art. Examples of suitable polyalkylene succinic anhydrides for use herein are thermal PIMA (polyisobutcnyl 5uccinic anhydride) dcscribPd in US, Patent N. 3,361,673;

chlorinated PIBSA described in U.S. Patent No. 3,172,892: a mixture of thermal and chlorinated PIBSA described in U.S. Patent No. 3,912,764; high succinic ratio PlBSA
described in U.S. Patent No. 4,234,435; polyPIBSA described in U.S. Patent Nos, 5,112,507 and 5,175,225; high succinic ratio polyPIBSA described in U.S. Patent NV5,

5,565,528 -dud 5,616,668; free radical PIBSA described in U.S. Patent Nos. 5,286,199, 5,i 19,030 and 5,625,004; PIBSA made from high methylvinyliclene polybutene described in U.S.
Patent Nos. 4,152,499, 5,137,97 and 5,137,980; high succinic ratio PIBSA madc from high methylvinylidene polybutene described in European Patent Application Publication No. EP
333 895; terpolymer PIBSA described in U.S. Patent No. 3,792,729, sulfonic acid PIBSA
described in U.S. Patent No. 5,777,025 and European Patent Application Publication No. EP
542 380; and purified PIBSA described in U.S. Patent No. 5,523,417 and European Patent Application Publicntinn No FP 602 S63, the contents of each of these references being incorporated herein by reference.
[00138) Non-nitrogen containing ashiess dispersant5 include derivative5 of polyalkylene succinic anhydrides such as, for example, succinic acids. Group 1 and/or Group 11 mono- or di-metal salts or sucenue acids, suceinate esters formed by the reaction of a polyalkylene succinic anhydride, acid chloride, or other derivatives with an alcohol (e.g..
HOR1 wherein RI is an alkyl group of from I to 10 carbon atoms) and thc likc and mixtures thereof.
[001391 If desired, the foregoing polyalkylene succinic anhydride ashless dispersants and/or non-nitrogen-containing ashless dispersants can be post-treated with a wide variety of post-treating reagents. For example, the foregoing polyalkylene succinie anhydride and/or non-nitrogen-containing ashless dispersants can be reacted with a cyclic carbonate under conditions sufficient to cause reaction of the cyclic carbonates with a hydroxyl group. The reaction is ordinarily conducted at temperatures ranging fium about 0 C to about 250 C, or from about 100 C to about 200 C or from about 50 C to about I80 C.
[001401 The reaction may be conducted neat, wherein the polyalkylene succinie anhydride ur ashless dispersant and the cyclic carbonate arc comhined in the proper ratio, either alone or in the present of a catalyst (e.g,, an acidic, basic or Lewis acid catalyst). Examples of suitable catalysts Include, but are not limited to, phosphoric acid, boron trifluoricic, alkyl or aryl sulfonic acid, alkali or alkaline carbonate.
The same solvents or diluents its described above with respect to the preparing the polyalkylene succinic anhydride may also be used in the cyclic carbonate post-treatment. In onc preferred embodiment, a cyclic carbonate for use herein is 1,3-dioxolan 2 one (ethylene cat bonate).
[001411 Nitrogen-containing basic ashless (metal-free) dispersants contribute to the base number or BN (as can be measured by ASTM 13 2896) of a lubricating oil composition to which they arc added, without introducing additional sulfated ash. The basic nitrogen compound used to prepare the colloidal suspensionsth 0. r .-c present invention must unitain basic nitrogen as measured by ASTM D664 test or D2895. It is preferably oil-soluble. The basic nitrogen compounds are sele.oted from the group consisting of snocinlmIdes, polysuceinimides, carboxylic acid amides, hydrocarbyl monoamines, hydrocarbon polyam int s, Mannieh condensation products of hydrocarbyl-substitutcd phenols, formaldehyde and polyamines other than the Ivlannich reaction product discussed herein above, phosphoramides, thiophosphoramicies, phosphonamides, dispersant viscosity index improvers, and mixtures thereof. These basic nitrogcn-containing compounds are described below (keeping in mind the reservation that each must have at least one basic iiitiogen). Any ot the nitrogen-containing compositions my he post-treated with, e.g., boron, using procedures well known in the art 50 long as the compositions continue to contain basic nitrogen.
1tm1421 The succinimide and polysiiceinimirle ashleA dispersants tharean he used in the lubricating oil compositions of the present invention are disclosed in numerous references and are well known in thc art. Certain fundamental types of succinimides and the related materials encompassed by the term of art "suceinimide are taught in, for examp)e, U.S. Pat.
Nos, 3,219,666; 3,172,892; 3,272,746; 4,234,435 and 6,165;235, the contents of which are incorporated by reference herein. Succinic-bascd dispersants have a wide variety of chemical structures. One OM of suceinie-bnsed dispersanis iiiay be rupresented by the formula:
sk\C¨C¨R1 õN4 R2¨ N1-1-1¨

H¨y¨s = "Ne-(:-13 of wherein each R' is independently a hydrocarbyl group, such as a polyolefiriLderived group.
Typically the hydrocarbyl group is an alkyl group, such as a polyisohutyl group.
AlLornaiively expressed, R1 groups ual 1 cunidui about 40 to about 500 carbon atoms, and these fitoms may be present in aliphatic forms. R2 is an a lkylene errinp, commonly an ethylene (C21-14) group.
[00143] Thc polyalkencs from which thc substitucat groups arc dcrivcd arc typically hornopnlymers and interpolymers polymeri7ahle olefin monomers of 2 to about 16 carbon atoms, and usually 2 to 6 carbon atoms. The amines which are reacted with the suceinie acylating agents to form the carboxylic dispersant composition can be monoamincs or po Iyam hies.
[001441 The term "succinimide" is understood in the art to include many of rhe amide, imide, and amidine species which may also be formed. The predominant product, however, is a blicCillif fl ilk and tin5turn] has been generally accepted as meaning the product of a reaction of an alkenyl substituted suc,c,inic acid nr anhydride with a nitrogen-containing compound. In one preferred embodiment, a succinimide, because of its commercial availability, arc those succinimicics preparcd from a hydrocarbyl suecinic anhydride, wherein the hydrocarhyl group contains from about 24 to about 350 carbon atom, and an ethylene amine or polyamine, the ethylene amines being especially characterized by ethylene diamine, diethylenc triaminc, tricthylcne tctramine, tetraethylene pentamine, and higher molecular wcighl polyethylene amines. Particularly permed are those succinimides prepared from polyiscibutenyl succinic anhydride of 70 to 128 carbon atoms and tetraethylene pentamine or higher molecular weight polyethylene amines or mixtures of polyethylene amines such that thc average molecular weight of thc mixture is about 205 Daltons. In one embodiment of the present invention, an ashless dispersant for use in the lubricating oil composition is a his-suceinimide derived ttom a polyisobutenyl group having a number average molecular weight of about 700 to about 2300.
[00145] Also included within the term "sucoinimide" arc thc co-oligomcrs of a hydrncarhyl succinic acid or anhydride and a polysecondary amine containing al least uric tertiary amino nitrogen in addition to two or more secondary amino groups.
Ordinarily, this composition has between 1,500 and 50,000 average molecular weight. A typical compound would be that prepared by reacting polyisobutenyl suecinie anhydride and ethylene dip iperazine.
[00146] If desired, the foregoing suceinimides and polysueeinimide ashless dispersants um, be post-treated with a wide variety of post-trezding reagents, e.g., with a cyclic carbonate, AA CiiAnAAed hereinahove. The resulting post-treated product has one or more nitrogens or the polyamino moiety substituted with a hydroxy hydrocarbyl oxycarbonyl, a hydroxy poly(oxyalkylcnc) oxyearbonyl, a hydroxyallcylene, hydroxyalkylenepoly(oxyalkylene), or mixture thereof.
[00141 The foregoing succinimides and polystiminimides, including the post-treated compositions. described above, can also be reacted to form berated dispersants. In addition to boric acid, examples of suitable boron compounds include boron oxides, boron halides and esters of boric acid. Cienerally, from about 0.1 equivalent in hnut 1 equivalent of boron compound per equivalent of basic nitrogen or hydroxyl in the compositions of this invention may be employed, [00148] Carboxylic ucid amide ushlosh dispersants arc also useful nitrogen-containing ashless dispersants. Typical of such compounds are those disclosed in ifs.
Patent No.3,405,064, the contents of which are incorporated by reference herein.
These compounds are ordinarily prepared by reacting is carboxylic acid Cr anhydride or ester thereof, having at least 12 to about 350 aliphatic carbon atoms in the principal aliphatic chain and. if desiied.
having sufficient pendant aliphatic groups to render the molecule nil soluble with an amine or a hydrocarbyl polyaminc, such as an ethylene amine, to give a mono or polyearboxylic acid amide. In one embodiment, a carboxylic amide L2111 be prepared from (I) a carboxylic acid of the formula R2COOH, where R2 is Cm_ualkyl or a mixture of this acid with a polyisobutenyl carboxylic acid in which the polyisobutenyl group contains from -/2 to 128 carbon atoms and (2) an ethylene polyaminc, especially triethylene tetramine or tetraethylene pentamine or mixturcs thereof.
[00149] Another class of useful nitrogen-containing ashless dispersants are hydrocarbyl monoarnines and hydrocarbyl polyarnines, preferably of the type disclosed in U.S. Patent No. 3,574,576, the contents of which are incorporated by reference herein. The hydrocarbyl group, which is preferably alkyl, or olefinic having one or two sites of unsaturation, usually contains from 9 to about 350, or from about 20 to about 200 carbon atoms. In one embodiment, suitable hydrooarbyl polyamines are those which are derived, e.g., by reacting polyisobutenyl chloride and a polyalkylene polyaminc, such as an ethylene amine, e.g., ethylene diamine, diethylene triamine, tetraethyl= pentamine, 2 aminoethylpiperazine, 1,1 propylene diamine, 1,2-propylenediamine, and the like.
(001501 Yet another class of useful nitrogen-containing ashIcsa dispersants is the Mannich compounds other than the Mannich reaction prodUet5 diwusseti lietein above.
These compounds are prepared from a phenol or U9,200 alkylphenol, art aldehyde, Knah as formaldehyde or formaldehyde precursor such as paraformaldehyde, and an amine compound. The amine may be a mono or polyamine and typical compounds arc prepared from an alkylamine, such as methylamine or an ethylene amine, such as, diethylenc lriarnirie, or tetraethylene pentamine, and the like. The phenolic material may be sultitrized and preferably is dodecylphenol or a CoodeQ alkylphenol, Typical Mannich bases which can be used in this invention are disclosed in U.S. Patent Nub. 3,539,663, 3,649,229;
3,368,972 and 4,157,309, the contents of which are incorporated by reference herein. U.S.
Patent No.
3,539,663, the contents of which are incorporated by reference herein, discloses Mannich bases prepared by reacting =an aikylphenol having at least 50 carbon atoms, preferably 50 to 200 carbon atoms with formaldehyde and an alkylene polyamine HN(ANH)I-1 where A i5 a saturated divalent alkyl hydrocarbon of 2 to 6 carbon atoms and n is 1-to and where the condensation product of said allcylene polyamine may be further reacted with urea or thiuurca. The utility uf these Maiiiiiuliit as sultan mate' ials foi preparing lubricating oil additives can Mn he significantly improved hy treating the Mannich base using conventional techniques to introduce boron into the compound.
[00151] Still yct another class of useful nitrogen-containing ashless dispersants is thc phosphoramides and phosphonam ides such as those disclosed in U.S. Patent Nos.
3,909,430 and 3,968,157, the contents of which are incorporated by reference herein.
These compounds may be prepared by forming a phosphorus compound having at least one P--N
bond. They can be prepared, fur example, by reacting phosphoius oxychloride with a hydrocarbyl diol in the presence of a monoamine or by reacting phosphorus nxyclikiride with a difunctional secondary amine and a mono functional amine. Thiophosphoramides eau be prepared by reacting an unsatulated hydiooailion compound containing from 2 to 450 Or morc carbon atoms, such as polyethylene, polylsobutylene, polypropylene, ethylene, 1-hexelic, 1,3-hexadiene, isobutyiene, 4-methyl- 1-pentene, and the like, with phnsphnnis pentasulfide and a nitrogen-containing compound as defined above, particularly an alkylamine, alkyldiamine, alkylpolyamine, or an alkyleneaminc, such as Cthylvie diamine, diethylenctriarnine, triethylenetetramine, tetraethylenepentamine, and the like.
[00152] Suitable ashless dispersants may also include amine dispersants, which are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines. Examples of such amine dispersants include those Jest:Jibed in, for example, U.S. Patent Not. 3,275,554, 3,438,757, 3,454,555 and 3,565,804, the contents of which arc incorporated by reference herein.
[00153] Suitable ashless dispersants may also be polymeric, which arc intcrpolymers of nil-soluhilizing mnnnmers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substitutes. Examples of polymeric dispersants include those described in, for example, U.S. Patent No.
3,329,658;
3,449,250 and 3,666,730, the contents of which arc incorporated by reference herein.
[00154] In general, the ashless dispersants will be present in the lubricating oil compositions of the present invention in an amount ranging from about 0.1 to about 10 wt. %, based on thc total weight of thc lubricating oil composition. In one embodiment, thc ashlcss dispersants will be present in the lubricating oil compositions ate present invention in an amount ranging from about 1 to about 8 wt. %, based on the total weight of the lubricating oil composition [00155] The lubricating oil compositions of the present invention may also contain other conventional additives that can impart or improve any desirable property of the.
lubricating oil composition in which these additives are dispersed or dissolved. Any additive known to a person of ordinary bkill in the an may be used in the lubricating oil compositions disclosed herein. Some suitable, additives have heen described in Mortier et al., "Chemistry and Technology of Lubricants", 2nd Edition, London, Springer, (1.996'); and Leslie R.
Rudnick, "Lubricant Additives: Chemistry and Applications", New York, Marcel Dekker (2003), both of which are incorporated herein by reference. For example, the lubricating oil compositions can be blended with antioxidants, anti-wear agents, detergents such as metal detergents, rust inhibitors, dchazing agents, elciniulsifying agents, metal deactivating agents, friction modillers, pour puha depressants, antifoamiag agents, co-solvents, package compatibilisers, corrosion-inhibitors, ashless dispersants, dyes, extreme pressure agents and thc likc and mixtures thereof. A variety of the additives are known and commercially available. These additives, or their analogous compounds, can be employed for the preparation of the lubricating oil compositions of the invention by the usual blending procedures.

[00156] In general, the concentration of each of the. additives in the iiibricatitT oil composition, when used, may range from about 0,001 wt. % to about 20 wt. %, from about 0.01 wt. % to about 13 ),vt, A, or from about 0,1 vvi. A lu about 10 wt. %, based on the total weight of the lubricating nil cnmpositinn.
[001571 The lubricating oil composition of the present invention can contain one or more antioxidants that can reduce or prevent the oxidation of the base oil, Any antioxidant known by a person of ordinary skill in the art may be used in the lubricatiau oil uomposition.
Non-limiting examples of suitable antioxidants include amine-based antioxidants (e.g., alkyl diphenylamines such as bis-nonylatcd diphenylaminc, bis-oetylatcd diphenylamine, and outylatedibutylated diplienylamine, pheityl-a-naplithylamine, alkyl or arylalkyl substituted phenyl-u-naphthylamine, a lkylatPri p-phenyl ene diamines, tetramethyl-d i arn nod i phenylarnine and the like), phenolic antioxidants (e.g., 2-tert-butylphenol, 4-2,4,6-tri-ter1-buty1phcnol, 2,6-di-tert-butyl-p-eresol, 2,6-di-tert-hutylphenol, 4,4'-methylneh1s-(2,6-di-ten-huty1phenot), 4,4'-thiobis(6-di-tert-butyl-v-cresol) and the like), sulfur-based antioxidants (e.g., dilaury1-3,3'-thiodipropionate, sulfurized phenolic antioxidants and the like), phosphorous-based antioxidants (e, g., phosphites and the like), zinc dithiophospliate, oil-suluble coppei compounds and combinations thereof. The amount of the antioxidant may vary from about 0.01 wt. % to about 10 wt. %, from about 0.05 wt. 14 to about 5 wt. %, or from about 0,i wt_ 14 to about 2 wt. 14, based on the total weight of the lubricating oil composition.
1001581 The lubricating oil composition of the present invention can contain a detergent. Metal-containing or ash-forming detergents function as both detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life, Detergents generally comprise a polar head with a lung hydrophobic tail. =1 he polar head comprises a metal salt of an acidic organic compound. The , salts may contain a sithstantially Rini h nmerri a amount of the metal in which case they are usually described as normal or neutral salts. A large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide).
[001591 Detergents that may be used include oil-soluble neutral and overbased sulfonates, phonatos, sulfurizcd phenatcs, thiophosphonatcs, salicylatcs, and naphthenates and other oil-soluble carboxylates of a uietal, paiticularly the alkali 01 alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium. The most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and inixtuics of calcium and/or magnesium with sodium.
[00 I 601 Commercial products are generally referred to as neutral or overbased.
Overbased metal detergents are generally produced by carbonating a mixture of hydrocarbons, detergent acid, for example: sulfonic acid, carboxylate etc., metal oxide or hydroxides (for example calcium oxide or calcium hydroxide) arid protilotcts such as xylcne, methanol and water. tor example, for preparing an overbased calcium stilfonate, In carbonation, the calcium oxide or hydroxide reacts with the gaseous carbon dioxide to form calcium carbonate. The sulfunic acid is neutralized with an excess of CaO or Ca(011)-i, to form The salfonare.
1001611 Overbased detergents may be low overbased, e.g., an overbased salt having a ON below 100. In one embodiment, the DN of a low overbased salt may be from about 5 to about 50_ In another embodiment, the BN of a tow overbased salt may be frum abuut 10 to about O. In yet another embodiment, the BN of a low overbased salt may he from about 15 to about 20.
1001621 Overhand detergents may be medium overbased, e.g., an overhand salt having a BN from about 100 to about 250. lit one embodiment, the BN of a medium overbased salt may be from about IOU to about 200. In another embodiment, the BN Of A
medium overbased salt may be from about 125 to about 175.
[00163] Overbused detergents may be high overbased, e.g., an overbased salt having a I3N above 250. In one embodiment, the 13N of a high overbased salt may be from about 7.50 to about 550.
1001641 In onc embodiment, the detergent can be one or more alkali or alkaline earth metal salts of an alkyl-substituted hydroxyarematic carboxylic acid.
Suitable hydroxyaromatie compounds include mononuclear rnonohydroxy and polyhydroxy aromatic, hydrocarbons haying 1 to 4, and preferably 1 to 3, hydroxyl groups.
Suitable hydroxyaruniatic compounds include phenol, catechul, ieoicinol, hydroquirionc, pyrogallol, crecnl, and the like. The preferred hydroxyaromatic compound is phenol.
[001651 The alkyl substituted moiety of the alkali or alkaline earth metal salt of an ailyl-substitutcd hydroxyarornatie carboxylic acid is derived from an alpha olefin having frnm about 10 to ahrun 80 carbon atoms. The olefins employed may be linear, isurricriLed linear, branched or partially branched linear. The olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched linear or a mixture of any of the foregoing.
[1191tit51 In one emhorliment, the mixture rut linear olefins that may be used is a mixture of normal alpha olefins selected from olefins having from about 12 to about 30 carbon atoms per molecule. In one embodiment, the normal alpha olefins are isomcrized Using at least one of a solid or liquid catalysi.
[Dill tol In another emhodirnent, the olefins are a branched olefinic propylene limner or mixture thereof having from about 20 to about 80 carbon atoms, i.e., branched chain olefins derived from the polymerization of propylene. The olefins may also be substituted with other functional groups, such as hydroxy groups, carboxylic acid groups, heteruatoins, arid the like, In one embodiment, the branched olefinie propylene oligomer or mixtures thereof havc from about 20 to about 60 carbon atoms. In one embodiment, the branched oleflnic propylene oligomer or mixtures thereof have from about 20 to about 40 uarbun atoms.
[00168] In one embodiment, at least about 75 mole% (e.g., at least about 80 mole%, at least about 85 mok%, at least about 90 mole%, at least about 95 molc%, or at lcaat about 99 mole%) of the alkyl groups contained within the alkali or alkaline earth metal Sall. of an alkyl-substituted hydroxyaromatic carboxylic acid such as the alkyl groups of an alkaline earth metal salt of an alkyl-substituted hydroxybentoic acid detergent arc a C2v or higher. In another embodiment, the alkali or alkalinc mirth nictal salt of an alkyl-substitutcd hydroxyaromatic carboxylic acid is an alkali or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid that is derived from an alkyl-substituted hydroxybenzoic acid in which the alkyl groups arc the rcsiduc of normal alpha-olcems containing at least 75 mole% C20 or higher normal alpha-olefins.
[00169] In another embodiment, at least about 50 mole % (e.g., at least about 60 mole %, at least about 70 mole %, at least about 80 mole %, at least about 85 mole %, at least about 90 mole %, at lca5t about 95 mole %, or at least about 99 molc %) of thc alkyl groups contained within the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatie carboxylic acid such as the alkyl groups of an alkali or alkaline earth metal salt of an alkyl-substituted hydroxybenz,oic acid are about C14 to about C18.
[00170] Thc resulting alkali or alkaline earth metal salt of au alkyl-substituted hydroxyaromatic carboxylic acid will he a mixture Af ortho and para isomers.
In one embodiment, the product will contain about 1 to 99% ortho isomer and 99 to 1%
para isomer.
In another embodiment, die pruduut will contain about 5 to 70% oitho and 95 to 30% para isomer.

[00171J 'lhe alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid can be neutral or overbased. Generally, an overbased alkali or alkaline earth metal salt Urd11 alkyl-substituted hydroxyarunlinic iiibuylic acid 15 one in which the 13N of The alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaramatic carboxylic acid has been increased by a process such as the addition of a base source (e.B., lime) and an acidic overbasing compound (e.g., carbon dioxide).
[00172} Sulfonates may he prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons.
Examples included those obtained by alkylating benzene, toluene, xyleue, naphthalene, diphcnyl or their halogen derivatives. The alkylation may be carried out in the presence, of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms. The alkaryl sullonates usually uuntniii from about 9 to about 80 oi more carbon atoins, preferably from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety.
1001731 The oil soluble sulfonates or alkaryl sulfonic acids may he neutralized with oxides, hydroxides, alkoxides, carbonates, earboxyIate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal. The amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from about 100 to about 220 wt. %
(preferably at least about 125 wt. %) of that stoichiornetrically required.
1001741 Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or ovorinued pioducts may be obtained by methods well known in the art. Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalidc, to form products which ale generally mixtures of compounds in which 7 or more phennlq are bridged by snifur containing bridges.

[00175] Generally, the amount of the additional detergent can be from abrnit 0.001 wt.
% to about 25 wt. %, from about 0.05 wt. % to about 20 wt. %, or from about 0.1 wt. % to about 15 wt. A,' based on the total weiglit of the lubricating oil composition.
[00l7ii] The lubricating oil composition of the present invention can contain one or more friction modifiers that can lower the friction between moving parts. Any friction modifier known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable friction modifiers include fatty carboxylic acids; derivatives (e.g., alcohol, esters, borated esters, amides, metal salts and the like) of fatty carboxylic acid; mono-, di or tri alkyl substituted phosphoric acids or phosphonic acids; derivatives (e.g., esters, amides. racial salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di- or tri-alkyl substituted amines;
mono- or di-alkyl substituted amides and combinations thereof. In some embodiments cxamples of friution modifiers iiiclude, but arc not limited to, alkoxylated fatty amines;
hnrated fatty epox ides, fatty phosphltes, fatty epoxides, fatty amines, borate(' allwxyLated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty imidazol ines as disclosed in U.S. Patent No. 6,372,696, the contents of which are incorporated by reference herein; friction modifiers obtained from a roactiun product of a C4 to C75, or a Co to C24, or a C6 to C20, fatty acid ester and a nitrogen-anntainina compound selected from thc group consisting of ammonia, and an alkanolantine and the like and mixtuies thereof. The amount of the friction modifier may vary from about 0,01 wt. % to about 10 wt, %, from about 0,05 wt. /n to about 5 wt. %, or from about 0.1 wl. % to about 3 wt, %, based on the total weight of the lubricating oil composition, [001771 The lubricating oil composition of the present invention can contain one or more anti-wear agents that can reduce friction arid exuessive wear. Any anti-wcar agcnt known by a person of ordinary skill in the. art may be used in the.
lubricating nil composition.

Non-limiting examples of suitable anti-wear agents include zinc dithiophosphate, metal (e.g., Pb, Sb, Mo and the like) salts of dithiophosphates, metal (e.g., Zn, Pb, Sb, MD and the like) salts of dithiucarbamates, metal (e.g.,Zn, Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine It of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acids and combinatious thereof. The amount of the anti-wear agent may vary from about 0.01 wt.
% to about 5 wt %, from about 0.03 wt. % to about 3 wt. %, or from about 0,1 wt. % to about 1 wt. u/9, based on the total weight of the lubricating oil composition [00178] In certain embodiments, the anti -wear agent is or comprises a dihydrocarbyl dithiophosphate metal salt, such as zinc dialkyl dithiophosphate cumpimuds.
The metal of the dihydrocarbyl dithiophosphate metal salt may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. In some embodiments, the metal is Linc. In other embodiments, the alkyl group of the dihydrocarbyl dithiophoaphate metal call ha from ahnut I to about 22 carbon atoms, from about 3 to about 18 carbon al.OMS, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the alkyl group is linear or branched.
[00179] The amount of the dihydrocarbyl tliihiophospbate metal salt including, the zinc dialkyl dithiophosphate salts in the lubricating oil composition disclosed herein is measured by its phosphorus content. In some embodiments, the phosphorus content of the lubricating oil 1.;outpositiurt disclosed herein Ls from about 0.01 wt. % to about 0.14 wt., based on the total weight of the lubricating oil composition, [001801 The lubricating oil composition of the present invention can contain one or more foam inhibitors or anti-foam inhibitors that can break up foams in oils.
Any foam inhibitor or anti-foam known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable foam inhibitors or anti-foam inhibitors include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers (e.g., polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methaerylate polymers, polyalkoxyamines arid combinations thereof.
In some. embodiments, the foam inhibitors or anti-foam inhihitorg comprises glycerol monostearate, polyglycol palmitate, a trialkyl monothiophosphate, an ester of sulfonated ricinoleici acid, benzoylaectone, methyl salicylate, glycerol rnonooleate, or glycerol dioleate.
The amount of the foam inhibitors or anti-foam inhibitors may vary from about 0.001 WI, %
to about 5 wt. %, from about 0.05 wt. % to about 3 wt. %, or from about 0.1 wt. % to about 1 wt. %, bascd on tho total weight of the lubricating oil composition_ [00181] The lubricating oil composition of the present invention can contain one or more pour point depressants that can lower the pour point of the lubricating oil composition.
Any pour point depressant known by a person of ordinary skill in the art may be used in the.
lubricating oil composition. examples of suitable pour point depressants include. polyrnethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, di(tetra-paraffin phenol)phthalate, condensates of tetra-paraftin phenol, condensates of a chlorinated paraffin with naphthalene and combinations thereof. hi some embodiments, the pour point depressant comprises an ethylene-vinyl metalc cupulymel, a condensate of chlorinated paraffin and phenol, polyalkyl styrene or the like. The amount of the pour point depressant may vary from about 0.01 wt. % to about 10 wt. %, from, about 0.05 wt, % to about 5 wt. Vci, ur from about 0.1 wt. % to about 3 wt, Q/O, based on thc total weight of the lubricating oil composition.
1001821 in one embodiment, the lubricating oil composition of the present invention does not contain one or more demulsifiers. In another embodiment, the lubricating oil composition or the present invention can cijnl,aiii WM or JIWIC cicmulsificrs that can promote oil-water separation in lubricating oil compositions that are exposed to water or steam. Any demulsifier known by a person of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting examples of suitable demulsifiers include anionic surfactants alkyl-naphthalene SUMJnates, alkyl belicene sulfonates and thc like), nonionic alkoxylateci alkyl phenol resins, polymers of alkylene oxides (e.g., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble acids, polyoxyethylcnc sorbitan ester and combinations thereof. The amount of the demillsifier may vary from about 0.01 wt. % to about 10 wt. %, from about 0.05 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 3 wt. %, based on the total weight of the lubricating oil composition.
[00183] Thc lubricating oil .Nripositiori of the present invention can contain one or more corrosion inhibitors that can reduce. corrosion. Any corrosion inhibitor known by a person of ordinary skill in the art may bc used in the lubricating oil composition. Non-limiting examples of suitable concision inhibitor include half esters or amides of dodecylsucclnic acid, phosphate esters, thiophosphates, alkyl imiduzulines, Suruusilics and combinations thereof. The amount of the corrosion inhibitor may vary from about 0.01 wt. %
to about 5 wt. %, from about 0.05 wt. %to about 3 wt, %, or from about 0.1 wt.
% to about 1 wt. %, based on the total weight of the lubricating oil composition, [001841 The lubricating oil composition of the present invention can contain one or more extreme pressure (EP) agents that can prevent sliding metal surfaces from seizing under conditions of cx-treme prc5sure. Any extreme pressure agent known by a person of ordinary skill in the art may he used in the lubricating oil composition. Generally, the extreme pressure agent is a compound that can combine chemically with a metal to form a surface film that prevents the welding of asperities in opposing metal surfaces under high loads.
Non-limiting examples of suitable extreme pressure agents include sulfurizcd aninuil or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially 54 =

esteritled esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysul fides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, 5ulfurizcd or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized hlends nf fatty acid, fatty acid ester and alpha-olefin, functinnally-qubstituted dihydrocarbyl polysultides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurizcd blends of tcrpcno and acyclic olefins, and polystil fide vleCto products, amine salts of phosphoric acid esters or thiophosphoric acid esters and combinations thereof. The amount of the extreme pressure agent may vary frnm about 0.01 wt. % to about 5 wt. %, from about 0.05 wt. % to about 2 wt. %, or from about 0.1 wt. % to about 1 wt, based on the total weight of thc lubricating oil composition.
[00 I 8.5] The lubricating nil composition of the present invention can contain one or more rust inhibitors that can inhibit the corrosion of ferrous metal surfaces.
Any rust inhibitor known by a peraon of ordinary skill in the art may be used in the lubricating oil composition. Non-limiting cxamples uf suitable rust inhibitors include nonionic polyoxyalkylene agents, e.g., polyoxyethylene lauryl ether, polyoxyethylene, higher alcohol ether, polyoxyethylenc nonylphonyl ether, polyoxyethylene octylphenyl ether, polyoxyethylenc octyl steacyl ether, polyoxyethylone ley] ether, polyoxycthylenc sorbitol monostearate, polyoxyethylene sorbitol monoolcate, and pulyciltylenc glycol monooleate;
stearic acid and other fatty acids; dicarboxylic acids; metal soaps; fatty acid amine salts;
metal salts of heavy sulfonic acid; partial carboxylic acid ester of polyhydric alcohol;
phosphoric esters; (short-chain) alkenyl SUCCilliC acids; partial esters thereof and nitrogen containing derivatives thereof; synthetic alkarylstilfonates, e.g., metal dinonylnaphthalene sulfonates; and the like and mixtures thereof. The amount of the rust inhibitor may vary from about 0.01 wt. % to about 10 wt. %, from about 0.05 wt. % to about 5 wt. %, or from about 0.1 wt. 'VD to about 3 wt. %. based on the total weight of the lubricating oil composition.

[00186] The lubricating oil composition of the present invention can contain one or more multifunctional additives. Non-limiting examples of suitable multifunctional additives include sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymulybderium organophosphorodithioate, oxymolybdenum monoglyeeride, oxymolybdenum diethylate amide, amine-molybdenum complex compound, and aulfo-oontaining molybdenum complex compound, [00187] The lubricating oil composition of the present invention can contain one or more viscosity index improvers. Non-limiting examples of suitable viscosity index improvers include, but arc not limited to, olefin copolymers, such as ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrenc-isoprene polybutene, po]yisobutylene, polymethacrylates, vinylpyrrolidnne and methactylate copolymers and dispersant type viscosity index improvers. These viscosity modifiers can optionally be grafted with grafting materials such as, for example, malcie anhydride, and the grafted material can be reacted with, for example, amines, amides, nitrogen-containing heterocyclic compounds or alcohol, to form multifunctional viscosity modifiers (dispersant-viscosity modifiers). Other examples of viscosity modifiers include star polymers (e.g., a star polymer comprising isoprene/styrene/isoprene triblock), Yet other examples of viscosity modifiers include poly alkyl(meth)acrylates of low ftronlr-fielci viscosity and high shear stability, functionalized poly alkyl(meth)acrylates with dispersant properties of high Brookfield viscosity and high shear stability, polyisobutylene having a weight average molecular weight ranging from 700 to 2,500 Daltons and mixtures thereof. The amount of the viscosity index improvers may vary from about 11.0 i wt. Lyn to ahout 25 wt. from about 0.05 wt. % to about 20 wt. CYO, or from about 0.3 wt, % to about 15 wt. %, based on the total weight of the lubricating oil composition.

1.0018SJ The lubricating oil composition of the present invention can contain one Or more metal &activators. Non-limiting examples of suitable metal deactivators include disalicylidene propylenediamine, triazole derivatives, thiaditizole derivatives, and mercaptoben7i m irla7nleA_ 1001891 IF desired, the at least one Mannich reaction product (b) and/or at least one ashless dispersant (c) may be provided alone or together as an additive package or concentrate in which the at least one Mannich reaction product (h) and/or at least one ashless dispersant (c) and optionally with the foregoing lubricant additives are incorporated into a substantially inert, normally liquid organic diluent such as, for example, mineral oil, naphtha, benLerie, toluene or xylene to form an additive concentrate. These concentrates usually contain from about 20% to about 80% by weight of such diluent. Typically, a neutral oil having a viscosity of about Ito about 8.5 cSt at 100T and preferably about 4 to about 6 cSt al I OTC will be used as the diluent, though synthetic oils, as well as other organic liquids which are compatible with the additives and Finished lubricating oil can also be used. The additive package will typically contain one or more of the various additives, referred to above, in the desired amounts and ratios to facilitate direct combination with the requisite amount of the oil of lubricating viscosity.
'the lubricating oil composition disclosed herein is usefi to lubricate an internal combustion engine such as a spark ignition engine, or a compression ignition diesel engine, c.g., a heavy duty diesel engine or a compression ignition diesel engine equipped with at least one of an exhaust gas recirculation (E013.) system; a catalytic comelier, and a particulate trap. Such a motor oil composition may be used to lubricate all major moving parts in any reciprocating internal combustion engine, reciprocating compressors and in steam engines of crankcase design. In automotive applications, the motor oil composition may also be used to cool hot engine parts, keep the engine free of rust and deposits, and seal thc rings and valves against leakage of combustion gases.
[001911 The primary sci viue ulasses foi a heavy duty diesel engine are light, medium, and heavy heavy-duty diesel engines as disclosed in ITS 40 CFR 86.090-2. The classification is based on factors such rts vehicle gross vehicle weight (GVW), vehicle usage and operating pattcins, other vehicle design characteristics, engine horsepower, and other engine design and operating characteristics. The following is a general description of the primary service classes for a heavy duty diesel engine:
[001921 (1) Light heavy duty diesel engines usually are non sleeved and riot designed for rebuild; their rated horsepower generally ranges from 7010 170. Vehicle body types in this group may include any heavy-duty vehicle built for a light-duty truck chassis, van trucks, multi-stop vans, recreational vehicles, and some single axle straight trucks.
Typical applications of such engines include personal tianspoitation, light-load commercial hauling and delivery, passenger service, agriculture, and cnnstniction. The engines In, this group are normally used in vehicles whose GVW is normally less than 19,500 lbs, [001931 (2) Medium heavy duty diesel engines may be sleeved or non-sleeved and may he. designed for rebuild; their rated horsepower generally ranges from 170 to 250. Vehicle body types in this group may include school buses, tandem axle straight trucks, city tractors, and a variety of special purpose vehicles such as small dump trucks, and trash compactor trucks. Typical app..eal..oris of such engines include commercial short haul and intra-city delivery and pickup. The engines in this group are normally used in vehicles whose (NW
varies from 19,500 to 33,000 lbs.
[001941 (3) Heavy heavy duty diesel engines are 5 lecvai and designed for multiple rebuilds; their rated horsepower generally exceeds 250. Vehicles body types in this grvup may include tractors, trucks, and buses used in inter-city, Jong-haul applications. The engines in this group are normally used in vehicles whose GVW exceed 33,000 lbs.
[00195] The following non-Limiting examples ate illustrative of the present invention.
[00196] Oil A, and Comparative. oils 1 and 2 were prepared FInd tested for piston cleanliness and tendency to piston ring sticking according to the Volkswagen 1 urbocharged D1 test, a European passenger car diesel engine test (CEC-L-78-T-99), which is part of the ACEA A/B and C soecilleatiolis piomulgatecl by the European Automobile Manufacturers Association in 2004 Ibis test was used to simulate repeated cycles of high-speed operation followed by idling, A Volkswagen 1.9 liter, inline, four cylinder turbocharged direct illjectitui auLuitiutin diesel engine (VW TDD was mounted on an engine dynamometer stand.
A 54-hour, 2-phased procedure that cycles between 30 minutes LIFO' C. oil WET
al idle and 150 minutes of 145 C oil sump at full power (4150 rpm) was carried out wirhnot intCriM oil top-ups. After the procedure, the pistons wore rated for carbon and lacquer deposits, as well Thr groove carbon tilling. The piston rings were evaluated for rinu ticking.
The results are set roan below in Table 111. Each of Oil A and Comparative Oils 1 and 7 were formulated to meet the specifications for SAE J100 revised November 2007 requirements for a multi-grade engine oil.
[011197] Oil A: A OW-20 viscosity grade fully formulated lubrieatinoil winpositioa was prepared comprising 79.23 wt. % Group III Base oil (4.1 cSt at 1005C), about 8 wt, A of an ethylene carbonate treated bis-succinimide dispersant, 3.0 wt.% of a Mannich reaction produet reautiun piuduct of a polyisobutyl- substituted phenol (prepared with a 1,000 number average molecular weight polyisobutylene having greater than 70 wt. %
methylvinylidene isomer), sodium giyeine, and formaldehyde), and typical amounts of detergents, phosphorous antiwear agent, antioxidant, friction modifier, foam inhibitor, viscosity index improver, pour point depressant, and diluent oil, Oil A had a sulfated ash content of about 0.79 M. u/o, sultUr content of about 0.18 wt. %, and a phosphorus content of about 0.074 wt. 9/0.
[00198] Comparative Oil 1; the formulation of Oil A was substuotially duplivated except that Comprative. Oil I had 707 wt % Group Ill Rase oil (4.1 cSt at I
00"C.) and L50 % of the Mannich reaction product. Comparative Oil I had a sulfated ash content of about 0.82 wt, %, sulfur content of about 0.18 wt, %, and a phosphorus content of about 0.07 wt. %. Comparative Oil 1 was a OW-20 viscosity grade I uhricatIng oil composition.
[00199J Comparative Oil 2: the formulation of Oil A was substantially duplicated except that Comparative Oil 2 had 79/ wt. % Group III Base oil (4.1 cSt at 100 C) and 2.25 wt. A of Lhe Ivlannich mac:lion produc.:1., Comparative Oil 2 had a sulfatcd ash content of about 0.79 wt. %, sulfur content of about 0.18 wt %, and a phosphorus content of about 0,07,1 wt. %, Comparative Oil 2 was a OW-20 viscosity grade lubricating oil composition, TABLE III
Test type: VWTIT2: SAR: OW-20 Measurements Oil A - Comp. Oil 1 Comp. Oil 2 Inspection 54 hours 54 hours 54 hours ?Clue and Avg 67 63 61 PC1nRL206 Avg 65 665-AvRS8R4P, ASP 0 0 , 0.31 4RngASF>=2.5 0 0 ASFG I RSIviAXme 0 0 2.5 ASFG2RSMAXme 0 0 0 Pass/Fail Pass VW Fail C3 Fail 0 [00200] The puss/fail sLure at:coaling Lu ACEA standards 134, 135, C3, and VW limits are listed in the following Table IV. if the VW 504/107 limits are passed then the remaining specifications are also passed.
TABLE IV

_ ____________________________________________________ ACEA ALEA

A3/Bel A5/B5 limits limits limits limits Piston Merit, Avg ?RI-206 ( RL206) ( -RL206) (iRL206+std) Ring sticking. Avg. 1st gr, AS, max.
Ring sticking. Max. 1st gr, <1.0 <1,0 ASF, max_ Ring sticking. Max_ 2nd gr, ASF, max.
. . __ TBN at EOT 6O 4,0 Report TAN at EOT Report Report Report [00201] It will bc understood that various modifications may be made to the embodiments disclosed herein. Therefore thc above dusviption should nut be construcd as limiting, but merely as exemplifications of preferred embodiments. For example, the functions described above and implemented as the best mode for operating the present invention arc for illustration purposes only. Other arrangements and methods may be implemented by those skilled in the art without departing from the scope and spirit of this invention. Moreover, those skilled in the art will envision other modifications within the scope and spirit of the claims appended hereto,

Claims

WHAT IS CLAIMED IS:

1. A lubricating oil composition comprising:
(a) greater than 65 wt. %, based on the total weight of the lubricating oil composition, of a base oil component having kinematic viscosity (Kv) at 100°C of 3.5 to 4.5 centistokes (cSt);
(b) 3.0 wt. % to 10 wt. %, based on the total weight of the lubricating oil composition, of at least one Mannich reaction product prepared by the condensation of a polyisobutyl-substituted hydroxyaromatic compound, wherein the polyisobutyl group is derived from polyisobutene containing at Ieast 70 wt. % methylvinylidene isomer and has a number average molecular weight of from 400 to 2,500, an aldehyde, an amino acid or ester derivative thereof; and an alkali metal base; and (c) at least one ashless dispersant other than component (b);
wherein the lubricating oil composition has a sulfur content of less than or equal to 0.30 wt.
%, a phosphorus content of less than or equal to 0.09 wt. %, and a sulfated ash content of less than or equal to 1.60 wt. % as determined by ASTM D 874, based on the total weight of the lubricating composition; and further wherein the lubricating oil composition is a multi-grade lubricating oil composition meeting the specifications for SAE J300 revised November 2007 requirements for a 0W-X multi-grade engine oil, wherein X is 20, 30, 40, 50, or 60.

2. A lubricating oil composition comprising;
(a) from 50 to 65 wt. %, based on the total weight of the lubricating oil composition, of a first base oil component having a kinematic viscosity (Kv) at 100°C of 3.5 to 4.5 centistokes (cSt);
(b) from 10 to 30 wt. %, based on the total weight of the lubricating oil composition, of a second base oil component having a Kv at 100°C of 5.5 to 6.5 cSt;

(c) 1.5 wt. % to 10 wt. %, based on the total weight of The lubricating oil composition, of at least one Mannich reaction product prepared by the condensation of a polyisobutyl-substituted hydroxyaromatic compound, wherein the polyisobutyl group is derived from polyisobutene containing at least 70 wt. % methylvinylidene isomer and has a number average molecular weight of from 400 to 2,500, an aldehyde, an amino acid or ester derivative thereof, and an alkali metal base; and (d) at least one ashless dispersant other than component (c);
wherein the lubricating oil composition has a sulfur content of less than or equal to 0.30 wt %
a phosphorus content of less than or equal to 0.09 wt. %, and a sulfated ash content of less than or equal to 1.60 wt. % as determined by ASTM D 874, based on the total weight of the lubricating oil composition; and further wherein the lubricating oil composition is a multi-grade lubricating oil composition meeting the specifications for SAE J300 revised November 2007 requirements for a 0W-X multi-grade engine oil, wherein X is 20, 30, 40, 50, or 60;
with the proviso that when the lubricating oil composition has a sulfated ash content of less than or equal to 0.60 wt.%, based on the total weight the lubricating oil composition, the Mannich reaction product is present in at least 3.0 wt. %, based on the total weight of the lubricating oil composition.

3. The lubricating oil composition of Claim 1 or 2, which is a SAE 0W-20 multi-grade lubricating oil composition or a 0W-30 multi-grade lubricating oil composition.

4. The lubricating oil composition of Claim 1 or 2, having a sulfur content of from 0.01 wt. % to 0.30 wt. %, a phosphorus content of from 0.01 wt. % to 0.07 wt.
%, and a sulfated ash content of from 0.10 wt. % to 0.8 wt. % as determined by ASTM D
874, based on the total weight of the lubricating oil composition.

5. The lubricating oil composition of Claim 1, wherein the base oil component Is a Group III base oil.

6. The lubricating oil composition of Claim 1, comprising 70 wL % to 85 wL. %
based on the total weight of the lubricating oil composition, of the base oil component having a kv at 100°C of 3.5 to 4.5 cSt.

7. The lubricating oil composition of Claim 1 or 2, wherein the polyisobutyl group of the polyisobutyl-substituted hydroxyaromatic compound is derived from polyisobutene containing at least 90 wt. % methylvinylidene isomer.

8. The lubricating oil composition of Claim 1 or 2, wherein the polyisobutyl group of the polyisobutyl-substituted hydroxyaromatic compound has a number average molecular weight in the range of from 500 to 2,500.

9. The lubricating oil composition of Claim 1 or 2, wherein the aldehyde is formaldehyde or paraformaldehyde, the base is an alkali metal hydroxide and the amino acid is glycine.

10. The lubricating oil composition of Claim 1 or 2, wherein the at least one Mannich reaction product is a the formula.

wherein each R is independently CHR' , wherein R' is branched or linear alkyl having one to 10 carbon atoms, cycloalkyl having from 3 carbon atoms to 10 carbon atoms, aryl having from 6 carbon atoms to 10 carbon atoms, alkaryl having from 7 carbon atoms to 20 carbon atoms, or aralkyl having from 7 carbon atoms to 20 carbon atoms, R1 is a polyisobutyl group derived from polyisobutene containing at least 70 wt. % methylvinylidene isomer and having a number average molecular weight in the range of 400 to 2,500;
X is hydrogen, an alkali metal ion, or alkyl having one carbon atom to about 6 carbon atoms;
W is -[CHR"]- m wherein each R" is independently II, alkyl having ono carbon atom to 15 carbon atoms, or a substituted-alkyl having one carbon atom to 10 Carbon atoms and one or more substituents selected from the group consisting of amino, amido, benzyl, carboxyl, hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide, or thiol; and m is an integer from one to 4;
Y is hydrogen, alkyl having one carbon atom to 10 carbon atoms, -CHR'OH, wherein R' is as defined above, or wherein Y' is -CHR'OH, wherein R' is as defined above; and R, X, and W are as defined above, Z is hydroxyl, a hydroxyphenyl group of the formula wherein R, R1, Y', X, and W are as defined above, and n is an integer from 0 to 20, with the proviso that when n = 0, Z must be:

wherein R, R1, Y', X, and W are as defined above.

11. The lubricating oil composition of Claim 1 or 2, wherein the at least one ashless dispersant is selected from the group consisting of s polyalkylene succinic anhydride ashless dispersant, a non nitrogen containing ashless dispersant and a basic nitrogen-containing ashless dispersant.

12. The lubricating oil composition of Claim 1 or 2, wherein the at least one ashless dispersant is present in an amount ranging from 0.1 wt. % to 10 wt. %, based on the total weight or the lubricating oil composition.

13. The lubricating oil composition of Claim 1 or 2, further comprising one or more lubricating oil additives selected from the group consisting of an antioxidant, detergent, rust inhibitor, dehazing agent, demulsifying agent, metal deactivating agent, friction modifier, antiwear agent, pour point depressant, antifoaming agent, co-solvent, package compatibiliser, corrosion-inhibitor, dye, extreme pressure agent and mixtures thereof.

14. The lubricating oil composition of Claim 1 or 2, which is a heavy duty diesel engine lubricating oil composition.