CA2184159A1

CA2184159A1 - Overbased alkyl oxy benzene sulfonates as detergents

Info

Publication number: CA2184159A1
Application number: CA002184159A
Authority: CA
Inventors: William F. King; Richard J. Nelson
Original assignee: Individual
Current assignee: Chevron Phillips Chemical Co LP
Priority date: 1994-12-28
Filing date: 1995-12-07
Publication date: 1996-07-04
Also published as: DE69531043T2; EP0748365B1; JPH09511015A; WO1996020265A1; EP0748365A4; DE69531043D1; EP0748365A1

Abstract

A marine lubricating oil has a major amount of oil of lubticating viscosity; and a minor amount of an overbased, alkyl oxy benzene sulfonate having a TBN of at least 200. Betwxn 40 wt.% and 80 wt.% of the alkyl group is attached at the 4-position and higher positions of the alkyl group. The oxy group can be hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy.

Description

2 1 8 ~ 1~ 5 9 PCT/US9~/16162 OVERBASED ALKYL OXY BENZENE
SULFONATES AS DETERGENTS
The present invention relates to an additive especially useful in a marine lubricating oil.
BACKGROUND OF THE INVENTION
U.S. 3,523,898 teaches that overbased alkyl phenol sulfonic acids are useful as d~ "Is in lubricating oils. The alkyl groups appear to be attached at either the 1- or 2- position of the alkyl groups, and the TBN
appears to limited to 150 or less.
British 1,372,532 teaches that mixtures of overbased, alkyl hydroxy benzene sulfonates and alkylsalicylic acids are useful in lubricating oils. The alkyl groups of the sulfonates appear to be attached at either the 1- or 2-position of the alkyl groups. The TBN appears to be about 200.
British 1,332,473 teaches that overbased, alkyl hydroxy benzene sulfonates are useful as an oil-soluble disl~e~s~ in lubricating oils. The patent is silent as to where the alkyl groups are attached. The TBN appears to be about 400, with a very high base ratio.
U.S. 4,751,010 teaches that partial sulfonation of alkylphenol results in the formation of an alkyl hydroxy benzene sulfonate that can be overbased using sulfurization and carbonation. The patent is silent as to where the alkyl groups are attached. The TBN appears to be in the range of from 200 to 250.
U.S. 5,330,663 and 5,330,664 teach overbased alkylphenoxy sulfonates that have alkyl groups derived from substantially straight-chained olefins that are either internal or alpha. It does not teach using olefins that are partially internal olefins.
U.S. Patent Nos. 3,523,898; 4,751,010; 5,330,663; and 5,330,664 are all hereby illc~l~o,~ed by reference for all purposes.

W096120265 2 ~ ~ 4 T 59 -2 - PCT/US95/16162 SUMMARY OF THE INVENTION
The present irlvention provides a lubricating oil having a major amount of base oil of lubricating viscosity; and a minor amount of an overbased, alkyl 5 oxy benzene sulfonate having a TBN of at least 2û0, preferably at least 250, between 40 wt.% and 30 wt. % of the alkyl group is attached at the 4- position and higher positions o, the alkyl group. Preferably, between 45 wt.% and 70 wt. % of the alkyl groul~ is attached at the 4- position and higher positions ofthe alkyl group. This lubricating oil is especially useful as a marine 10 lubricating oil.
The oxy group can be either hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy. Preferably, it is hydroxy.
Preferably, the alkyl group of the overbased, alkyl oxy benzene sulfonate has from eighteen to thirty carbon atoms per alkyl group. More preferably, it has from twenty to twenty-four carbon atoms per alkyl group.
One process for making this overbased, alkyl oxy benzene sulfonate comprises alkylating an oxy benzene with an olefin between 40 wt.% and 80 wt. % internal olefins to produce an alkyl oxy benzene, then sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and overbasing the alkyl oxy benzene sulfonic acid to produce the overbased, alkyl oxy benzene sulfonate. Preferably, the internal olefin is produced by isu~ ;"g an olefin using an iron p~"lacdli~ul lyl catalyst.
In an alternative e,llbodi",~"l of the present invention, an additive is produced by alkylating an oxy benzene with a polyalpha olefin having an activity of at least 80% to produce an alkyl oxy benzene, sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid, and overbasing the alkyl oxy benzene sulfonic acid to produce an overbased, alkyl oxy benzene suifonate having a TBN of at least 200, preferably at least 250.
DETAILED DESCRIPTION OF THE INVENTION

In its broadest aspect, the present invention involves highly overbased, alkyl oxy benzene sulfonate de~ ly~ where at least 40 wt.% of the alkyl groups are attached at the 4- position and higher positions of the ~i W096/20265 ~1 84 i 59 PcTlus95ll6l62 alkyl group. When at least 40 wt.% of the alkyl groups are attached at the 4-position and higher position, the viscosity is lowered si~"irl~a"lly.
On the other hand, at least 20 wt.% of the alkyl groups should be 5 attached at the 1-, 2-, and 3- position in order to reduce high temperature deposit formation. While Applicants do not wish to be bound by any particular theory of operation, it is believed that too high of internal dlla.,l I~ l leads to structures that are similar to materiais derived from branched olefins. Such materials tend to decompose readily at the 1 o branch jng, In one e"lL)o~ii"l~l ,l, between 40 wt.% and 80 wt. % (preferably between 45 wt.% and 70 wt. %) of the alkyl group is attached at the 4-position and higher positions of the alkyl group. This type of additiYe can be 15 produced by alkylating an oxy benzene with an olefin co, lldil lil ,g between between 40 wt.% and 80 wt. % internal olefins to produce an alkyl oxy benzene, sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and overbasing the alkyl oxy benzene sulfonic acid to produce the overbased, alkyl oxy benzene sulfonate. An olefin co,~Ldi"i"g between 20 20 wt.% and 60 wt. % internal olefins can be formed by isu~ 9 an alpha oiefin using an iron pe"~dcd,l"~"yl catalyst.
In another embodiment, the additive is produced by alkylating an oxy benzene with a polyalpha olefin having an activity of at least 80% to produce 25 an alkyl oxy benzene, sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and overbasing the alkyl oxy benzene sulfonic acid to produce an overbased, alkyl oxy benzene sulfonate having a TBN of at least 250.
The present invention comes out of work in trying to find an inexpensive alternative to the use of salicylates in lube oils for marine ,, '; ' ~s. That alternative should have a TBN of over 250, have a viscosity of less than 600 cSt, and have uulll,udldLi~e properties with uo"",le,uial salicylates.

3~
The initial attempts were with an overbased oxy benzene sulfonate having a linear C20-C28 alkyl group. That material turned out to be so viscous W096120265 21 ~i ~ l 5~9 PCT/IJS95/16162 1 that its viscosity could not be measured. It was so viscous that it didn't flow from a beaker even wl1en left overturned for over a weekend.
We overcame this problem by using an overbased alkyl oxy benzene 5 sulfonate haYing alkyl groups that were isol "t~ prior to alkylation of the benzene. it is essential that alkyl groups of the overbased alkyl oxy benzene sulfonate be pl t:dul "i, IdLt~ly attached at the 4- position and higher positions of the alkyl group.
1 û THE OVERBASED ALKYL
OXY BENZENE SULFONATE
The lubricating oil has a minor amount of an overbased, alkyl oxy benzene sulfonate having a TBN of at least 2ûû, preferably at least 250, wherein at least 4û wt % of the alkyl group of the sulfonate is attached at the 4- position and higher positions of the alkyl group. The oxy group can be either hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy.
Preferably, it is hydroxy.
By UTBN,~ we r~ean UTotal Base Number," which refers to the amount of base equivalent to one milligram of KOH in one gram of additive. Thus, higher TBN numbers reflect more alkaline products and therefore a greater alkalinity reserve. The Total Base Number for an additive .,o,,,,uoaiLion is readily determined by ASTM test method D664 or other equivalent methods.

By Uinternal olefins,~ we mean an olefin wherein the double bond is at the 4- position and higher positions of the alkene, instead of at the 1-, 2-, or3- position.
Preferably, the alkyl group of the overbased, alkyl oxy benzene sulfonate has from eighteen to thirty carbon atoms per alkyl group. More preferably, the alkyl group has from twenty to twenty-four carbon atoms per alkyl group.
The additive o~ the present invention can be produced by alkylating an oxy benzene with an olefin UUI ILdil lil ll~ between 40 wt.% and 80 wt. % internal olefins to produce an alkyl oxy benzene, sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and overbasing the alkyl oxy i-- WO 96/2026S 2 1 8 ~ 1 5 9 PcTlusgsll6l62 benzene sulfonic acid to produce the oYerbased, alkyl oxy benzene suifonate. An olefin cu, I~dil 1;119 between 40 wt.% and 80 wt. % intemal olefins can be formed by isomerizing an alpha olefin using an iron pe"ldca, L~o, Iyl catalyst.

The p,ucesses of alkylating an alkyl oxy benzene with an olefin to produce an alkyl oxy benzene, and sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene suifonic acid are both discussed in detail in U.S. Patent Nos. 5,330,663 and 5,330,664, which have been incorporated by reference for all purposes. Our alkylation and sulfonation p, ucesses differ only in the olefins used and reaction time. In our batch alkylation reaction, we need only about six to eight hours. The preferred sulfonation process is a falling film process using a charge mole ratio of sulfur trioxide to alkylphenolof 1.1:1 and a reaction temperature in the range of from 70 to 1û0C C, followed by illl",e~lid~ neul,dli~dliull.
A neutralized slurry of alkyl oxy benzene sulfonic acid is added to a slurry of xylenes, methanol, and calcium hydroxide. The resulting slurry is then Cdl bC/IldL~:d during which a second slurry of alkyl oxy benzene sulfonic acid and a second slurry of xylenes, methanol, and calcium hydroxide are added. After the carbonation, the material is stripped to remove methanol and water. Lube oil is then added and the solids removed. The remainder of the solvents are then stripped off and additional lube oil added to adjust the product to the final base number.

THE LUBRICATING OIL PRODUCT
The oil-soluble, highly overbased, alkyl oxy benzene sulfonate additive co,,,p~siliu, ,s produced by the process of this invention are useful lubricating oil additives imparting detergency and di~l.e,:,e,lcy properties when added to the lubricating oil Colll,uosiliu" employed in the crank case of an internal combustion engine. Such lubricating oil c~",~u~silio"s comprise a major amount of base oil of lubricating viscosity; and a minor amount of oil-soluble, highly overbased, alkyl oxy benzene sulfonate additive ~u" I~OO::IiiiUl IS. These - 35 lubricating oil compositions are useful in diesel engines, gasoline engines, as well as in marine engines.

W0 96/20265 2 1 ~ ~ 1 5 9~ PCTIUS9S/16162 1 Such lubricating oil cu,,,uo~i[iu,,s employ a hnished lubricating base oil oil of lubricating viscosity which may be single or multigrade. Multigrade lubricating base oils are prepared by adding viscosity index (Vl) improvers.
Typical viscosity index improvers are polyalkyl methacrylates ethylene and 5 propylene copolymers styrene-diene copolymers and the like.
The lubricating base oils used in such co",l-osiliu, 15 may be mineral oils or synthetic oils of ~iscosity suitable for use in the crank case of an internal combustion en3ine such as gasoline engines and diesel engines 10 which include marine e~gines. Crank case lubricating oils ordinarily have a viscosity of about 1300 cSt at 0 F to 24 cSt at 210 F (99 C). The lubricating base oils maY be derived from synthetic or natural sources.
Mineral oils for use as the base oil in the invention includes paraflinic lld,l.)~ , and other oils that are ordinarily used in lubricating oil cullluo~iLio,ls. Synthetic oils include both h~dlucdlboll synthetic oils and synthetic esters. Usef~l synthetic h~dl UCdl UUI I oils include liquid polymers of a-olehns having the pr4per viscosity. Especially useful are the h~dl uyel ,dled liquid oligomers of C6 to C12 a-olefins such as 1-decene trimer. Likewise alk~lue"~"es of proper viscosity such as didodecyl benzene can be used.
20 Useful synthetic esters include esters of both l,,u, lO~,dl uu~ylic acids andpolycarboxylic acids as well as monohydroxy alkenols and polyols. Typical examples are didodecyl adipate pentaerythritol I~LId~apludlt: di-2-ethylhexyl adipate dilaurylsebacate and the like. Complex esters prepared from mixtures of mono and clicarboxylic acid and mono and dihydroxy alkanols can 25 also be used Blends of h~dlu~dlboll oils with synthetic oils are also useful. For example blends of 10 to 25 wt. % hydrogenated 1-decene trimer with 75 to 90 wt. % 150 SUS (10~ F) mineral oil gives an excellent lubricating base oil.

In one ~",Lodi",~"l the lubricating oil also has an ashless diau~l~dllL
and a zinc dialkyldithiol~hosphate.
In another ~",uo.li",~"l the lubricating oil also has a detergent 35 selected from the group consisting of metal phenates metal sulfonates and metal salicylates.

WO 96120265 2 1 8 4 ~ 5 9 PCTIUS95/16162 Other additives which may be present in the formulation include rust inhibitors, foam inhibitors, corrosion inhibitors, metal deactivators, pour point de~ sa"Ls, anti-oxidants, and a variety of other well-known additives More ~,ueuirically, the following additive c~"l,uol~c"~:, examples of Cu~,uul ,e, l~ that can be faYorably employed in CUI"~i, IdLiol, with the overbased, alkyl oxy benzene sulfonate of the present inYention ( 1 ) Metallic ~ l y~, ILa. overbased sulfurized alkyl,ul ~elld~es, overbased sulfonates, and overbased salicylates.
1û (2) Ashless diapel~dll~. alkenyl succinimides, alkenyl suc-,i"i",ides modified with other organic compounds, and alkenyl suc"i"i",ides modifled with boric acid, alkenyl succinic ester.
(3) Oxidation inhibitors 1 ) Phenol type phenolic) oxidation inhibitors: 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methyl-6-tert-butylphenol), 2,2'-(methylenebis(4-methyl-6-tert-butyl-phenol), 4,4'-butylidc~ bis(3-methyl-6-tert-butylphenol), 4,4'-isopropylidenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl4-methylphenol, 2,6-di-tert-butyl4-ethylphenol, 2,4-dimethyl-6-tert-butyl-phenol, 2,6-di-tert-a-dimethylamino-p-cresol, 2,6-di-tert-4-(N.N' dimethyld",i"~",~l,ylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3-methyl~-hydroxy-5-tert-butylbenzyl)-sulfide, and bis (3,5-di-tert-butyi-4-hydroxybenzyl).
2) Diphenylamine type oxidation inhibitor: alkylated diphenylamine, phenyl-a-naphthylamine, and alkylated a-naphthylamine.
3) Other types: metal ~ io~,d~bal~d~ (e.g., zinc d;~lliocd~a~l~d~t:), and methylenebis (dibutyl~ l liOCd~ I-a"~d~
(4) Rust inhibitors (Anti-rust agents) 1 ) Nonionic polyoxyethylene surface active agents:
polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, poiyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethyiene sorbitol mono-oleate, and polye:hylene glycol monooleate.
2) Other compounds: stearic acid and other fatty acids, dicarboxilic acids, metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acid, partial carboxylic acid ester of polyhydric alcohol, and pllo:,ul~uri., ester.
(5) Demulsifiers: addition product of alkylphenol and ethyleneoxide, poloxyethylene alkyl ether, and polyoxyethylene sorbitane ester.

(6) Extreme pressure agents (EP agents): zinc dialkyldill liu,uho:,,ul Idle (Zn-DTP, primary alkyl type & secondary alkyl type), sulfurized oils, diphenyl sulfide, methyl Il iul 1101 U~l~dl d~ , ul llo~ il IdL~d lldj~ ILI ,al~ , benzyl iodide, fluoroalkyll~olysiloxane, and lead napl lll IdlldL~.

(7) Friction modifiers: fatty alcohol, fatty acid, amine, borated ester, and other esters (8) Multifunctional additives: sulfurized oxymolybdenum dillliocdlùdllldl~, sulfurized oxymolybdenum organo pllo:"ullulu dithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum complex compound, and sulfur-~u, ~Ld;l lil lO molybdenym complex compound (9) Viscosity illdex improvers polymethacrylate type polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and 2~ di~uc:l ~>dl 1~ type viscosity index improvers.

(10) Pour point depressants: polymethyl methacrylate EXAMPLES
The invention ~/ill be further illustrated by following examples, which set forth particularly advantageous method e"~uodi~"~ . While the Examples are provided to illustrate the present invention, they are not intended to limit it.
3~

W096/20265 21841~ PCT/US95116162 COMPARATIVE EXAMPLE
ALKYLATION USING NORMAL --OLEFINS
A. Preparation of Alkylated Phenols High overbased alkyl hydroxy benzene suifonates were prepared using an alkylphenol deriYed by ,u, ild-,Lil Iy 3.0 moles of phenol per each mole of a normal C20 to C24 a-olefin mixture using Amberlyst-36 catalyst [a polystyrene cross-linked sulfonic acid resin having a Hammett acid function 10 (Ho) of less than -2.2 and an acid number of 5.4 milliequivalents per gram].
Amberlyst-36 resin catalyst is c~ lui~lly available from Rohm & Haas, Pl,iladel,ul1ia, PA.
The olefin mixture had the following olefinic positions, ~ lll,i"ed by using a macro program using Nuclear Magnetic Resonance Spe~I, usc~, y (N'~AR).
wt. % Aloha wt. % Beta wt. % Internal wt. % Tri-substituted 89.1 0.5 1.4 0.3 The alkylation reactions were conducted at 1 0û C using a batch alkylation unit. The reaction time was six hours. Afterwards, the alkylated phenol was recovered by filtering and then stripping the excess phenol from 25 the product stream at 400C F and 1 torr. The recovered alkylphenol products were analyzed for monoalkyl and dialkyl content and ortho/para sl ,hctitl Itinn by superfluid ,illUllldlUyldUIly (SFC) and fourier transform infrared spectroscopy (FT-IR) respectively.
The results of the SFC analysis are set forth in the table below:
% olefin/parrafin 0.3 wt. %
% monoalkylate 86.7 wt. %
% dialkylate 12.6 wt. %
% phenol 0.1 wt. %

W096/20265 2 1 8 4 1 5.9: PCTIUS95/1616Z

The results of t~le FT-IR analysis for the monoalkylate are set forth in the table below:
% ortho 50.3 wt. %
% para 49.7 wt. %

The alkylphenol was analyzed using gas ~ nlld~o~l d~J~ly and mass s;~e~,l, u~ Ll y. Average positional dLLal,l " "~"l results for the C22 carbon are as follows:
P2 P3 P~ Ps P6 P7 Ps Ps P10 P1-49.84 17.80 9.99 4.65 4.47 3.47 2.95 261 2.17 2.04 B. Suifonation of Alkylated Phenols The alkylated phenol was sulfonated using a falling film reactor.
Reaction conditions were as follows:
Feed rate of al~ylphenol was 4.26 gms/min Charge mole ratio of sulfur trioxide to alkylphenol was 1.03:1 Air to sulfur trioxide ratio was 4:1 Reaction temperature was 90 C
Cyclohexamine analysis for this product indicates that a sulfonate as Ca value of 3.79 wt. ,'0 was obtained.
C. Nel. Ll ' ' on 380 grams of a~kylphenol sulfonic acids produced aoove were ;"""edidLely neutralized in a stirred beaker containing 320 grams xylenes, 16 grams methanol, and 32 grams calcium hydroxide.

D. Ov~ ai. .g 450 grams of Y~ylenes, 90 grams of methanol, and 138.5 grams of calcium hydroxide were added to a reactor and stirred for flve minutes. A
slurry made up of 190.0 grams of alkylhydroxy benzene sulfonic acid at 3.80 wt. % Ca as sulfonate, 160 grams xylenes, 8 grams methanol, and 16 grams calcium hydroxide, were then added to the reactor and stirred for 20 minutes.
The slurry was heated to 90 F during the 20 minute stir period. 79 grams of WO 96/20265 2 1 g 4 ~ 5 ~ PCIIUS95/16162 carbon dioxide was charged to the reactor over 130 minutes. The rate of addition of the carbon dioxide was gradually reduced from 0.76 grams per minute to 0.25 grams per minute oYer the Cdl bUI ,dLiun period. At 75% of the carbon dioxide charge, a second slurry made up of 190.0 grams of 5 alkylhydroxy benezene sulfonic acid at 3.8û wt. % Ca as sulfonate, 16û
grams xylenes, 8 grams methanol, and 16 grams calcium hydroxide was added. At 80/~ of the carbon dioxide charge, a slurry of 56 grams xylenes, 13 grams methanol, and 35.5 grams calcium hydroxide was added.
At the end of ca, UOIld~il)ll, the reactor was equipped with a cul~dc:l ,ser for stripping and the temperature was ramped to 200 F over two hours. At 200 F, the temperature was then ramped to 270 F over 30 minutes. At 270 F, 215 grams of 100 Neutral oil was added and the entire batch was then filtered through a Buchner filter. The filtrate was then stripped to 40û F at 40mm Hg vacuum. The base number was then measured with a resulting number of 318. An additional 45 grams of 100 Neutral oil was added to adjust the base number to 312.5.
The final product had a viscosity that was too viscous to measure at 100 C at a TBN of 312.5. It had 22.37% of the alkyl group of the sulfonate a~tached at the 4- position and higher positions of the alkyi group.

ALKYLATION USING ISOMERIZED OLEFINS
The procedures of the Comparative Example were repeated using a C20 to C2< olefin mixture isomerized by using iron pentacarbonyl ;~u",e,i~dliol~. This i~UIII~ dliUII process is known in the literature, and is disclosed in T. A. Manuel, Joumal of Organic Chemistry, 27, 3941 (1962).
The olefin mixture had the following olefinic positions, determined by usin~ a macro program using NMR.
wt. % Alpha wt. % Beta wt. % Intemal wt. % Tri-sl Ihstitl Ited 0.6 1 3.6 97 2.4 The alkylphenol was analyzed using gas ul ll Ull Id~Uyl d~ y and mass :~ue~l~ u,,,~l, y. Average positional dlldl~l 1111~11~ results for the C22 carbon are as follows:

W096120265 2 ~ ~ 1;5~ PCTIUS95/16162 P2 P3 Pi Ps P6 P7 Ps Ps P10 Pl1 3023 12~52 7.92 7.57 8.05 7.05 6.74 6.18 6.61 7.11 The final produc~ had a viscosity of 581 cSt at 100 C at a TBN of 300.5 It had 49.33 % of the alkyl group of the sulfonate attached at 4- position and higher positions of the alkyl group.

ALKYLATION USING l'OLYALPHA OLEFINS

The procedures of the Comparative Example were repeated using a polyalpha olefin derived from C,O dimer. The polyalpha olefin had the following olefinic posltions, determined by using a macro program using NMR.

wt. % Aloha wt. % Beta wt. % Internal wt. % Tri-substituted 14.0 13.4 29.8 56.0 The alkylphenol was analyzed using gas ~ UlI IdLuu~ uhy and mass 20 spectrometry Average positional attachment results for the C22 carbon are as folloWS:
P2 P3 Pl Ps P~ P7 Ps Pg P10 P11 48.0 16.0 7.6 7.2 5.9 5.2 4.5 3.4 2.3 0.0 The final product had a viscosity of 109 cSt at 100 C at a TBN of 296.
It had 28.45 % of the slkyl group of the sulfonate attached at 4- position and higher positions of the alkyl group.

Results of experiments for cu",pa,i~ the overbased phenoxy sulfonate of the invention with ~u,,,,,,~,~,lally available metal-containing L~ly~llL~ are shown below W0 96/20265 2 1 8 ~ 1 5 9 PCTIUSg51l6l62 Oxidation stability Test method: according to JIS K-2514 Tested d~le, ye, lls.
Example 1:0verbased phenoxy sulfonate of invention which is described in Example 1 of Sp~,iricdlio,~
Phenate l: Commercially available overbased phenate Phenate lI:Another ~u~ e~ ~ia:~y available overbased phenate Sulfonate: C~"""~ 'ly available overbased sulfonate Salicylate l:Co"l",eu,idlly available overbased salicylate Salicylate lI:Another commercially available overbased salicylate Oil for test: TBN 33 in SAE #40 Test c~ ilio,~s. heated at 165.5-C for 72 hours Results: set forth in the following table Metal-Containing Ratio of Viscosity (40 )C) Detergent (HeatedlUnheated) Example 1 1.06 Phenate 1 1.25 Phenate ll 1.22 Sulfonate 139 Salicylate 1 1.09 Salicylate ll 1.42 The above results show the improved oxidation stability of the phenoxy sulfonate of the invention.
D~l~,y~ .y at elevated temperature Test method: Hot tube test Oil for test: TBN 33 in SAE #40 Test conditions: 330 C, 16 hours Results: set forth in the following table WO 96~20265 2 1 8 4 ~ 5 9 - 14 - PCT/US9S/16162 Metal-Containing Detergent Laquer rating (10 = Clear)) Example 1 6.0 Phenate l 0 Phenate ll 6.0 5Sulfonate 0 Salicylate 1 6.0 Salicylate ll 6.0 The above results show the improved d~ yellcy of the phenoxy 10 sulfonate of the invention at an elevated temperature Thermal stabiiity Test method: Panel coker test Oil for test: TBN 33 in SAE #40 15Test ~,ul~di~iul ,s. 320 C, 3 hours Results: set forth in the following table Metal-Containing D~tergent Deposit (mg) Example 1 4û
20 Phenate 1 10 Phenate ll ~
Sulfonate 430 S21icylate 1 155 Salicylate !l 55 The above results show the improved thermal stability of the penoxy sulfonate of the invention.
Friction Coefficient 30Oil for test:
SAE 10W30 oil is prepared by compounding a succinimide ashless dispersant, a low overbased calcium sulfonate, zinc dialkyl~ iu~hus~lldlt:, and a viscosity index improver into 150 neutral oil. To the compounded oil is added the metal-cu, lldil lil lU deter~ent in an amount COI ~ UI l~il l9 to TBN 10.
Results: set forth in the following table wo 96/20265 2 1 8 4 1 ~ 9 PcTruss~/16162 Metal-Containing Friction Coefficient Detergent Example 1 0.100 0.087 Phenate 1 0.163 0.157 Phenate ll --Sulfonate 0.137 0.132 Salicylate I - _ Salicylate ll --The above results show the reduction of friction coefficient proved by the phenoxy sulfonate of the invention.
Stability in Water 15Test method: ASTM D-2619 (modified) Oil for test: TBN 33 in SAE #40 Test conditions: 100 9 of the test oil (its TBN is previously determined) and 5 g of distilled water are placed in a pressure-resistant bottle. The bottleis placed in an air thermostat at 93 C, for 24 hrs. under the condition that the20 bottle is rotated with upside down at 5 r.p.m., for hydrolyzing the test oil.The hydrolyzed test oil is then determined for its TBN. Decrease of TBN per the original TBN is ~ tP~
Results: set forth in the following table.
25Metal-Containing Detergent Decrease of TBN (%) Example 1 Phenate 1 70 Phenate l l 20 Sulfonate 30 30 Salicylate 1 Salicylate ll 6 The above results show the stability in water of the phenoxy sulfonate of the invention.

WO 96/2026~ 2 1 8 ~ 1 5 q ` PCT/US95/16162 EXAMPLES OF ADDITIVE PACKAGES
The following wt. ~/O is based on the amount of an active c~," ,~ e"L, namely, with neither process oil nor diluent oil. The phenoxy sulfonate 5 employed is that described in Example 1.
I. Marine Diesel Engine Oils 1 ) Phenoxy sulfonate 65.0 wt.%
Primary alkyl Zn-DTP 5.9 wt.%
Diluenl: oil 29.1 wt.%
2) Phenoxy sulfonate 64.0 wt.%
Alkenylsuccinimide ashless ~ c, IL 6.3 wt.%
Diluent oil 29.7 wt.%
3) Phenoxy sulfonate 59.0wL.%
Primary alkyl Zn-DTP 5.4 wt.%
Alkenylsuccinimide ashless di~ e,~d"L 5.9 wt.%
Diluent oil 29.7 wt.%
4) Phenoxy sulfonate 63.6 wt.%
Phenol type oxidation inhibitor 9.1 wt.%
Diluent oil 27.3 wt.%

5) Phenoxy sulfonate 53.5 wt.%
AlkylaLed diphenylamine-type oxidation inhibitor 16.3 wt.%
Diluent oil 30.2 wt.%

6) Phenoxy sulfonate 63.6 wt.%
Phenol-type u~iddLi~JI ,i, ll liLJi~ul 4.5 wt.%
Alkylated diphenylamine-type oxidation inhibitor 4.6 wt.%
Diluent oil 27.3 wt.%

~ WO 96~20265 2 1 8 4 1 5 9 PCTIUS95/16162 7)Phenoxy sulfonate 59.5 v~t.%
Primary alkyl Zn-DTP 5.4 wt.%
Phenol-type oxidation inhibitor 5.0 ~,vt.%
Diluent oil 30.0 v~h%
8)Phenoxy sulfonate 58.3 wt.%
Alkenylsuccinimide ashless di~ dl 11 5.8 Vlt.%
Alkylated diphenylamine-type oxidation inhibitor 8.3 ~vt.%
Diluentoil 27.5~vt.%
9)Phenoxy sulfonate 57.0 v~t.%
Primary alkyl Zn-DTP 5.2 Vlt.%
Alkenylsuccinic ester ashless ulapel ~a,ll 5.7 wt.%
Phenol-type oxidation inhibitor 2.1 v~t.%
Alkylated diphenylamine-type oxidation inhibitor 2.0 Vlt.%
Diluent oil 28.0 wt.%
2010) Phenoxy sulfonate 46.2 v~t.%
Overbased sulfurized alkylphenate 20.8 wt.%
Diluent oil 44.0 wt.%
11 ) Phenoxy sulfonate 37.0 wt.%
25Overbased sulfurized alkylsalicylate 28.0 wt.%
Diluent oil 35.0 v~t.%
12) Phenoxy sulfonate 58.9 Vlt.%
Overbased sulfonate 4.7 Vlt.%
30Primary alkyl Zn-DTP 6.5 wt.%
Diluent oil 29.9 v~t.%

13) Phenoxy su~fonate 48.3 v~t.%
Overbased sulfurized alkylphenate 14.7 wt.%
35Primary alkyl Zn-DTP 6.0 v~t.%
Diluent oil 31.0 v~t.%

WO 96/20265 2 1 8 4 1 ~ 9 PCT/US95/16162 14) Pheno~ysulfonate 18 40.8v~t.%
Overbzsed sulfurized phenate 17.5 v~t.%
Alkenylsuccinimide ashless ~ dl 11 6,7 wt.%
Diluent oil 35.0 wt.%

15) Phenoxy sulfonate 45.9 v~t,%
Overbased sulfurized phenate 11.5 wt.%
Alkenylsuccinic ester ashless disersant 4.9 v~t.%
Primary alkyl Zn-DTP 4.9 v~t.%
10Diluen~ oil 32,8 v~t,%

16) Phenoxy sulfonate 63.9 v~t.%
Overbased sulfurized alkylphenate 3.3 wt.%
Pheno'. type oxidation inhibitor 1.1 v~t.%
Alkylated diphenylamine-type oxidation inhibitor 1.0 v~t.%
Diluent oil 30.7 wt.%

17) Phenoxy sulfonate 51.6 v~t,%
20Overbased sulfurized alkylphenate 5.7 v~t.%
Primary alkyl Zn-DTP 3.3 v~t.%
Alkenylsuccinimide ashless dispersant 4.1 v~t.%
Alkyla~ed diphenylamine-type oxidation Inhibitor 1.6 vit.%
25Diluent oil 33.7 v~t.%

18) Phenoxy sulfonate 53.4 v~t.%
Primary alkyl Zn-DTP 3.4 wt.%
Alken~lsuccinimide ashless ui~e,~d~ 5.7 VJt,%
30Demu~sifier 5.7 wt.%
Diluent oil 31.8 v~t.%

19) Phenoxy sulfonate 47,0 v~t.%
Overbased sulfurized alkylphenate 16.0 v~t.%
35Primary alkyl Zn-DTP 2.5 v~t.%
Alkenylsuccinimide ashless di~ dll~ 3.4 v~t.%
Demulsifier 2.5 v~t,%
Diluent oil 28.6 wt,%

W096120265 2 1 ~ 4 1 5 9 PCT~S9S/I6l62 Il. Motor Car Engine Oils 1 ) Phenoxy sulfonate 25.3 wt.%
Alkenylsuccinimide ashless dispersant 35.9 wt.%
Primary alkyl Zn-DTP 11.2 wt.%
Diluent oil 27.6 wt.%
2) Phenoxy sulfonate 21.1 wt.%
Overbased sulfonate 8.6 wt.%
Alkenylsuccinimideashless dispersant 30.1 wt.%
Primary alkyl Zn-DTP 9.7 wt.%
Diluent oil 30.5 wt.%
3) Phenoxy sulfonate 18.9 wt.%
Alkenylsuccinimide ashless dispersant 39.6 wt.%
Secondary alkyl Zn-DTP 6.3 wt.%
DithiOCdl LJdl I IdLI~ type oxidation inhibitor 4.2 wt.%
Diluent oil 31.0 wt.%

4) Phenoxy sulfonate 14.9 wt.%
Overbased suifurized alkylphenate 3.8 wt.%
Alkenylsuccinimide ashless di~ dl ll 35.1 wt.%
Secondary alkyl Zn-DTP 6.4 wt.%
Phenol type oxidation inhibitor 4.3 wt.%
Diluent oil 35.~ wt.%
5) Phenoxy sulfonate 20.0 wt.%
Alkenylsuccinimide ashless di~ al,~ 32.1 wt.%
Secondary alkyl Zn-DTP 7.1 wt.%
Di~l liO~.dl bdl I Idl~ type anti-wear agent 3.6 wt.%
Diluent oil 37.2 wt.%

2 1 ~ ~ 1, 5 9 WO 96120265 ; PCTIUS95/16162 6)Phenoxy sulfonate 7.4 wt.%
Overbased sulfurized dlkylphenate 8.4 wt.%
Basic sulfonate 3.7 wt.%
Succinimide ashless dial~cl ~dl 1l 31.6 wt.%
Secondary alkyl Zn-DTP 5.8 wt.%
Molybdenum-c~ dil lil l9 anti-wear agent 3.7 wt.%
Diluent oil 39.4 wt.%
7) Phelloxy sulfonate 17.7 wt.%
Alkenylsuccinimide ashless dia~ dlll 28.7 wt.%
Primary alkyl Zn-DTP 3.4 wt.%
Secondary alkyl Zn-DTP 5.0 wt.%
Alkylated diphenylamine-type oxidation inhibitor 5.7 wt.%
Dithlo~a~ ,d~ type anti-wear agent 0.9 wt.%
Diluent oil 38.6 wt.%
8) Phenoxy sulfonate 12.9 wt.%
Alkenylsuccinimide ashless dispersant 37.9 wt.%
Secondary alky! Zn-DTP 8.2 wt.%
Phenol type oxidation inhibitor 1.0 wt.%
Alkylated diphenylamine-type oxidation inhibitor 4.1 v~t.%
DiLllio~d,l,d~"d~e type anti-wear agent 1.0 wt.%
Demulsifier 0.9 wt.%
Boron-cu"ldi~ ,i"g friction modifier 2.1 wt.%
Diluent 31.9 wt.%

WO 96/20265 ~ l 8 4 1 ~ ~ PCT/US95/16162 Ill. Hydraulic Oils - 21 -1 ) Phenoxy sulfonate 4.6 wt.%
Primary alkyl Zn-DTP 64.5 wt.%
Phenol type oxidation inhibitor 6.6 wt.%
Pl los~l ~UI U~5-UUI lldil lil Ig extreme pressure agent 4.9 wt.%
Triazol type corrosion inhibitor 3.8 wt.%
Demulsifier 3.3 wt.%
1û Nonionic anti-rust agent 3.3 wt.%
Diluent oil 9.0 wt.%
2) Phenoxy sulfonate 2.3 wt.%
Basic sulfurized alkylphenate 2.5 wt.%
Primary alkyl Zn-DTP 49.6 wt.%
Phenol type oxidation inhibitor 7.3 wt.%
Sulfur-~u, I~dil lil l9 extreme pressure agent 6.0 wt.%
Triazol type corrosion inhibitor 3.4 wt.%
Demulsifier 5.0 wt.%
Nonionic anti-rust agent 3.0 wt.%
Diluent oil 13.9 wt.%
3) Pehonoxy sulfonate 12.2 wt.%
Phenol type oxidation inhibitor 14.8 wt.%
Diphenylamine type oxidation innibitor 7.4 wt.%
Sulfur-cu, l~dir lil l9 extreme pressure agent 4.5 wt.%
Pl lospl~ol uus-containing extreme pressure agent 39.2 wt.%
Triazol type corrosion inhibitor 1.0 wt.%
Demulsifier 7.0 wt.%
Nonionic anti-rust agent 4.5 wt.%
Diluent oil 9.4 wt.%

wos6l2o265 2 1 84 1 59 PcT~USssll6l62 4) Phenoxy sulfonate 8.5 wt.%
Overbased salicylate 3.7 wt.%
Phenol type oxidation inhibitor 13.5 v~t.%
Diphenylamine type oxidation inhibitor 8.2wt.%
Sulfur-c:ul lldi~ ,g extreme pressure agent 4.5 wt.%
Phosphorous-containing extreme pressure agent 42.7 v,lt.%
Triazol type corrosion inhibitor 1.2 vtt.%
Demulsiher 6.5 wt.%
Nonionic anti-rust agent 4.3 wt.%
Diluent oil 6.9 v~t.%
IV. Tldlls",issiu,~ Hydraulic Fluids 1 ) Phenoxy sulfonate 35.9 v~t.%
Primar~l alkyl Zn-DTP 20.9 wt.%
Polyoi ~ype friction modifier 17.9 wt.%
Sulfur-~o,l~di"i"g extreme pressure agent 5.8 v~t.%
Diluent oil 19.5 v~t.%
2) Phenoxy sulfonate 28.8 v~t.%
Basic sulfonate 11.3 v~t.%
Primary alkyl Zn-DTP 16.7 v~t.%
Amide type friction modifier 13.9 v~t.%
Sulfur~ dil lil l9 extreme pressure agent 6.0 vit.%
Diluent oil 23 3 v~t.%

~ WO 96/20265 2 1 8 4 1 ~ 9 PCTIUS95116162 3) Phenoxy sulfonate 32.2 wt.%
Primary alkyl Zn-DTP 18.9 wt.%
Alkenylsuccinimide ashless dispersant 0.5 wt.%
Amide type friction modifier 10.4 wt.%
Ester type friction modifier 13.9 wt.%
Pl ,~spilu, u~s, Sulfur-co, ILdil ~il 19 extreme pressure agent 6.3 wt.%
Diluent oil 17.8 wt.%
0 4) Phenoxy sulfonate 23.6 wt.%
Basic sulfonate 10.1 wt.%
Overbased salicylate 2.4 wt.%
Primary alkyl Zn-DTP 15.2 wt.%
Polyol type friction modifier 0.4 wt.%
Amide type friction modifier 8.4 wt.%
Phosphorous, Sulfur-co~ ~Idil ,i"y extreme pressure agent 5.1 wt.%
Diluent oil 23.6 wt.%
While the present invention has been described with reference to specific embodiments, this dlJplicdlioll is intended to cover those various changes and substitutions that may be made by those skilled in the art without departing from the spirit and scope of the appended claims.

Claims

What is claimed is:

1. An additive comprising an overbased, alkyl oxy benzene sulfonate having a TBN of at least 200, wherein between 40 wt.% and 80 wt. % of the alkyl group is attached at the 4- position and higher positions of the alkyl group, and wherein the oxy is selected from the group consisting of hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy.

2. An additive according to Claim 1 wherein the overbased, alkyl oxy benzene sulfonate is produced by a process comprising:
(a) alkylating an oxy benzene with an olefin having between 40 wt.%
and 80 wt. % internal olefins to produce an alkyl oxy benzene;
(b) sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and (c) overbasing the alkyl oxy benzene sulfonic acid to produce the said overbased, alkyl oxy benzene sulfonate.

3. An additive produced by a process comprising:
(a) isomerizing an olefin using an iron pentacarbonyl catalyst to produce an isomerized olefin;
(b) alkylating an oxy benzene with the isomerized olefin to produce an alkyl oxy benzene, wherein the oxy is selected from the group consisting of hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy;
(c) sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and (d) overbasing the alkyl oxy benzene sulfonic acid to produce an overbased, alkyl oxy benzene sulfonate having a TBN of at least 200.

4. An additive produced by a process comprising:
(a) alkylating an oxy benzene, wherein the oxy is selected from the group consisting of hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy, with a polyalpha olefin having an activity of at least 80% to produce an alkyl oxy benzene;
(b) sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene sulfonic acid; and (c) overbasing the alkyl oxy benzene sulfonic acid to produce an overbased, alkyl oxy benzene sulfonate having a TBN of at least 200.

5. An additive according to Claim 1, 3, or 4 wherein the overbased, alkyl oxy benzene sulfonate has a TBN of at least 250.

6. An additive according to Claim 1 or 3 wherein between 45 wt.% and 70 wt. % of the alkyl group is attached at the 4- position and higher positions of the alkyl group.

7. An additive according to Claim 1, 3, or 4 wherein the oxy group is hydroxy.

8. An additive according to Claim 1, 3, or 4 wherein the alkyl group has from eighteen to thirty carbon atoms per alkyl group.

9. An additive according to Claim 8 wherein the alkyl group has from twenty to twenty-four carbon atoms per alkyl group.

10. A lubricating oil comprising:
(a) a major amount of base oil of lubricating viscosity; and (b) a minor amount of the additive according to Claim 1, 3, or 4.

11. A lubricating oil according to Claim 10 wherein the lubricating oil is a marine lubricating oil.

12. A lubricating oil according to Claim 10 further comprising an ashless dispersant and a zinc dialkyldithiophosphate.

13. A lubricating oil according to Claim 10 further comprising a viscosity index improver.

14. A lubricating oil according to Claim 10 further comprising a detergent selected from the group consisting of metal phenates, metal sulfonates, and metal salicylates.