Process for preparing high overbased metal sulfurized alkylphenates, wherein a majority of the alkalinity is provided by at least a stoichiometric excess of metal. The process is characterized by a sulfurization reaction using a promoter, followed by overbasing with carbon dioxide, a polyamine, and additional metal base in the presence of an alkylene glycol under reactive conditions at temperatures in the range of about from 150.degree. C. to 190.degree. C. The process affords a metal sulfurized phenate product which is substantially insensitive to overcarbonation, which exhibits low corrosive wear, and which exhibits high rates of acid neutralization. These compositions are useful in the formulation of marine cylinder lubricants.

The present invention relates to processes and methods for preparing high 
overbased sulfurized alkylphenate compositions, which are substantially 
insensitive to overcarbonation, which exhibit low corrosive wear, and 
which exhibit high rates of acid neutralization. These compositions are 
useful in the formulation of marine cylinder lubricants. 
BACKGROUND OF THE INVENTION 
Group II metal overbased sulfurized alkylphenate compositions (sometimes 
referred to as "overbased phenates") are useful lubricating oil additives, 
which impart detergency and dispersancy properties to the lubricating oil 
composition, as well as providing for an alkalinity reserve in the oil. 
Alkalinity reserve is necessary in order to neutralize acids generated 
during engine operation. Without this alkalinity reserve, the acids so 
generated would result in harmful engine corrosion. 
The preparation of overbased phenates is well known in the art and is 
described, for example, in U.S. Pat. Nos. 2,680,096; 3,178,368; 3,367,867; 
3,801,507; and the like. The disclosures of each are incorporated herein 
by reference in their entirety. Typically, overbased phenates have been 
prepared by combining, under elevated temperatures, an alkylphenol, a 
neutral or overbased hydrocarbyl sulfonate, a high molecular weight 
alcohol, lubricating oil, a Group II metal oxide, hydroxide or C.sub.1 to 
C.sub.6 alkoxide, sulfur, and adding a polyol, typically an alkylene 
glycol, to the heated mixture. The water of reaction is removed and carbon 
dioxide added. Uncombined CO.sub.2 is removed and the reaction vessel is 
then further heated under vacuum to remove the alkylene glycol, water, and 
the high molecular weight alcohol. The product is overbased by 
incorporation therein of hydrated lime and carbon dioxide. Typically an 
alkylene glycol is used to promote both the neutralization and 
sulfurization, and also to facilitate overbasing. 
U.S. Pat. No. 4,248,718 discloses the preparation of lubricating oil 
additives in which a nitrogen-containing compound (such as a polyamine) is 
combined with a basically reacting metallic compound, a suspending agent 
(such as sulfurized alkylphenates), and a chalcogen compound (such as 
carbon dioxide). In their material, at least a third of the alkalinity 
value derives from the nitrogen-containing compound, and there is only 
from 0.05 to 0.5 equivalents of basically reacting metallic compound per 
equivalent of suspending agent. 
A problem is encountered in the preparation of high overbased phenates. The 
problem occurs in the overbasing step, in which carbon dioxide is added to 
the phenate to increase the Total Base Number in the final product. During 
this overbasing step, it is well known in the art that, in general, high 
overbased phenates are very sensitive to the addition of too much carbon 
dioxide (overcarbonation). The result of adding too much carbon dioxide is 
the production of a product with varying quality. 
SUMMARY OF THE INVENTION 
The present invention is based, in part, on our discovery that sulfurized 
alkylphenates can be advantageously prepared which are substantially 
insensitive to overcarbonation, which exhibit low corrosive wear, and 
which exhibit high rates of acid neutralization. These compositions are 
obtained by modifying the overbasing step by the inclusion of a polyamine 
concurrently with the carbon dioxide. 
A metal overbased sulfurized alkylphenate composition, having a TBN of at 
least 200, wherein a majority of the alkalinity is provided by at least a 
stoichiometric excess of metal, is prepared by contacting an alkylphenol 
with sulfur, in the presence of a promoter, and from 1.7 to 2.7 moles of a 
metal base per mole of the alkylphenol to neutralize the alkylphenol and 
the promoter under reactive conditions. This contacting step is carried 
out for a sufficient period of time to react essentially all of the 
sulfur. The reaction product of that contacting step is contacted with 
carbon dioxide and additional metal base, if required to provide the 
desired TBN, in the presence of an alkylene glycol having 2 to 6 carbon 
atoms and a polyamine under reactive conditions at temperatures in the 
range of about from 160.degree. C. to 190.degree. C. 
The alkylphenol should have at least one alkyl substituent having from 9 to 
36 carbon atoms, and the alkylene glycol should have from 2 to 6 carbon 
atoms. 
Preferably, the first step of the process is conducted at temperatures in 
the range of about 120.degree. C. to 200.degree. C. More preferably, it is 
conducted using about from 0.8 to 3.5 moles of sulfur and from 0.025 to 2 
moles of promoter per mole of alkylphenol, and a minor amount of an inert 
organic liquid diluent. 
Preferably, the second step of the process is conducted in situ with the 
reaction product mixture of the first step. The second step is conducted 
using about 0.2 to 2 moles of carbon dioxide, about 0.1 to 0.9 moles 
polyamine, and 0.2 to 2 moles of alkylene glycol per moles of alkylphenol. 
Preferably, the alkylene glycol is ethylene glycol. 
Preferably, both steps are conducted at pressures in the range of about 
from 25 mm Hg absolute to 850 mm Hg absolute. 
Further aspects of the invention will be apparent from the following 
description. 
DETAILED DESCRIPTION OF THE INVENTION 
In its broadest aspect, the present invention involves a metal overbased 
sulfurized alkylphenate modified with at least one polyamine. 
Prior to discussing the invention in further detail, the following terms 
will be defined: 
DEFINITIONS 
As used herein, the following terms have the following meanings, unless 
expressly stated to the contrary: 
The term "Group II metal" or "alkaline earth metal" means calcium, barium, 
magnesium, and strontium. 
The term "metal base" refers to a metal hydroxide, metal oxide, metal 
alkoxide and the like and mixtures thereof, wherein the metal is selected 
from the group consisting of lithium, sodium, potassium, magnesium, 
calcium, strontium, barium, or mixtures thereof. 
The term "calcium base" refers to a calcium hydroxide, calcium oxide, 
calcium alkoxide, and the like, and mixtures thereof. 
The term "lime" refers to calcium hydroxide, also known as slaked lime or 
hydrated lime. 
The term "Total Base Number" or "TBN" refers to the amount of base 
equivalent to milligrams of KOH in 1 gram of sample. Thus, higher TBN 
numbers reflect more alkaline products, and therefore a greater alkalinity 
reserve. The TBN of a sample can be determined by ASTM Test No. D2896 or 
any other equivalent procedure. 
The term "overbased sulfurized alkylphenate composition" refers to a 
composition comprising a small amount of diluent (e.g., lubricating oil) 
and a sulfurized alkylphenate complex wherein additional alkalinity is 
provided by an excess of a metal oxide above the stoichiometric amount, 
hydroxide or C.sub.1 to C.sub.6 alkoxide, based on the amount required to 
react with the hydroxide moiety of the sulfurized alkylphenol. Generally a 
carbon dioxide treatment is required to obtain high TBN overbased 
sulfurized alkylphenate compositions, resulting in what is believed to be 
a complex of the phenate with a colloidal dispersion of metal carbonate. 
The term "promoter" refers to either: 
(a) alkanoic acids having 1 through 3 carbon atoms, i.e., formic acid, 
acetic acid, and propionic acid, and mixtures thereof, or 
(b) alkylene polyols having from 1 to 3 carbon atoms. 
The term "alkylphenol" refers to a phenol group having one or more alkyl 
substituents at least one of which has a sufficient number of carbon atoms 
to impart oil solubility to the resulting phenate additive. 
SYNTHESIS 
The present process can be conveniently conducted by contacting the desired 
alkylphenol with sulfur in the presence of a promoter and metal base under 
reactive conditions, preferably in an inert-compatible liquid hydrocarbon 
diluent. Preferably the reaction is conducted under an inert gas, 
typically nitrogen. In theory the neutralization can be conducted as a 
separate step prior to sulfurization, but pragmatically it is generally 
more convenient to conduct the neutralization and the sulfurization 
together in a single process step. 
The combined neutralization and sulfurization reaction is typically 
conducted at temperatures in the range of about from 100.degree. C. to 
250.degree. C., preferably 120.degree. C. to 200.degree. C., depending on 
the particular metal and promoter used. Based on one mole of alkylphenol, 
typically from 0.8 to 3.5, preferably from 1.2 to 2, moles of sulfur and 
about 0.025 to 2, preferably 0.1 to 0.8, moles of promoter are used. 
Typically about from 1.7 to 2.7 moles of metal base are used per mole of 
alkylphenol, including the base required to neutralize the promoter. The 
reaction is also typically conducted in a compatible liquid diluent, 
preferably a low viscosity mineral or synthetic oil. The reaction is 
preferably conducted for a sufficient length of time to ensure complete 
reaction of the sulfur. This is especially important where high TBN 
products are desired because the synthesis of such products generally 
requires using carbon dioxide together with polyols. 
Where the neutralization is conducted as a separate step, both the 
neutralization and the subsequent sulfurization are conducted under the 
same conditions as set forth above. Optionally specialized sulfurization 
catalysts, such as described in U.S. Pat. No. 4,744,921, the disclosure of 
which is hereby incorporated in its entirety, can be employed in the 
neutralization-sulfurization reaction. 
The sulfurized phenate product is overbased by carbonation. Such 
carbonation can be conveniently effected by addition of a polyol, 
typically an alkylene diol, e.g., ethylene glycol, and carbon dioxide to 
the sulfurized phenate reaction product. It is during this carbonation 
step that the polyamine is also added, simultaneously with the carbon 
dioxide and the polyol. The overbasing is typically conducted at 
temperatures in the range of above from 150.degree. C. to 190.degree. C., 
preferably 165.degree. C. to 180.degree. C., for about from 0.1 to 4 
hours. Conveniently, the reaction is conducted by the simple expedient of 
bubbling gaseous carbon dioxide through the reaction mixture. Excess 
diluent and any water formed during the overbasing reaction can be 
conveniently removed by distillation either during or after the reaction. 
Carbon dioxide is employed in the reaction system in conjunction with the 
metal base to form overbased products and is typically employed at a ratio 
of about from 0.5 to 3 moles per mole of alkylphenol, and preferably from 
about 0.8 to about 2 moles per mole of alkylphenol. Preferably, the amount 
of CO.sub.2 incorporated into the overbased sulfurized alkylphenate 
provides for a CO.sub.2 to metal weight ratio of about from 0.45:1 to 
about 0.75:1. All of the metal base, including the excess used for 
overbasing, is added in the neutralization step. 
Typically, the process is conducted under vacuum up to a slight pressure, 
i.e., pressures ranging from about 25 mm Hg absolute to 850 mm Hg absolute 
and preferably is conducted under vacuum to reduce foaming up to 
atmospheric pressure, e.g., about from 40 mm Hg absolute to 760 mm Hg 
absolute. 
Additional details regarding the general preparation of sulfurized phenates 
can be had by reference to the various publications and patents in this 
technology such as, for example, U.S. Pat. Nos. 2,680,096; 3,178,368 and 
3,801,507. The relevant disclosures and these patents are hereby 
incorporated by reference in their entirety. 
Considering now in detail, the reactants and reagents used in the present 
process, first all allotropic forms of sulfur can be used. The sulfur can 
be employed either as molten sulfur or as a solid (e.g., powder or 
particulate) or as a solid suspension in a compatible hydrocarbon liquid. 
Preferably, the metal base used is calcium hydroxide because of its 
handling convenience versus, for example, calcium oxide, and also because 
it affords excellent results. Other calcium bases can also be used, for 
example, calcium alkoxides. 
Suitable alkylphenols which can be used in this invention are those wherein 
the alkyl substituents contain a sufficient number of carbon atoms to 
render the resulting overbased sulfurized alkylphenate composition 
oil-soluble. Oil solubility may be provided by a single long chain alkyl 
substituent or by a combination of alkyl substituents. Typically the 
alkylphenol used in the present process will be a mixture of different 
alkylphenols, substituted with C.sub.9 to C.sub.32 alkyl carbon chain. The 
alkyl chain can be linear, branched, or mixtures thereof. 
The alkylphenols used are typically mixtures of para-alkylphenols and 
ortho-alkylphenols, although the predominance of either isomer can be 
used. Alkyl-hydroxy toluenes or xylenes, and other alkyl phenols having 
one or more alkyl substituents in addition to at least one long chained 
alkyl substituent can also be used. 
In general the present process introduces no new factor or criteria for the 
selection of alkylphenols and accordingly the selection of alkylphenols 
can be based on the properties desired for lubricating oil compositions, 
notably TBN and oil solubility, and the criteria used in the prior art or 
similar sulfurization overbasing process and/or processes. For example, in 
the case of alkylphenate having substantially straight chain alkyl 
substituents, the viscosity of the alkylphenate composition can be 
influenced by the position of an attachment on alkyl chain to the phenyl 
ring, e.g., end attachment versus middle attachment. Additional 
information regarding this and the selection and preparation of suitable 
alkylphenols can be had for example from U.S. Pat. Nos. 5,024,773, 
5,320,763; 5,318,710; and 5,320,762, all of which are hereby incorporated 
by reference in their entirety. 
If a supplemental sulfurization catalyst, such as for example desired in 
U.S. Pat. No. 4,744,921, is employed, it is typically employed at from 
about 0.5 to 10 weight % relative to the alkylphenol, and preferably at 
from about 1 to 2 weight %. In a preferred embodiment, the sulfurization 
catalyst is added to the reaction mixture as a liquid. 
The overbasing procedure used to prepare the high TBN overbased sulfurized 
alkylphenate compositions of this invention also employs a polyol, 
typically a (C.sub.2 to C.sub.4 alkylene glycol, preferably ethylene 
glycol, in the overbasing step, which is added simultaneously with the 
polyamine. 
The polyamines use in the invention having from about 2 to about 12 amine 
nitrogen atoms and from about 2 to about 40 carbon atoms. The polyamine 
preferably has a carbon to nitrogen ratio of from about 1:1 to about 10:1. 
The polyamine may be substituted with a substituent group selected from: 
(A) hydrogen; 
(B) hydrocarbyl groups from about 1 to about 10 carbon atoms; 
(C) acyl groups from about 2 to about 10 carbons; and 
(D) monoketo, monocyano, lower alkyl and lower alkoxy derivatives of (B) 
and (C). 
"Lower," as used in lower alkyl and lower alkoxy, means a group containing 
about 1 to 6 carbon atoms. "Hydrocarbyl" denotes an organic radical 
composed of carbon and hydrogen which may be aliphatic, alicyclic, 
aromatic or combinations thereof, e.g. aralkyl. The acyl groups falling 
within the definition of the aforementioned (C) substituents are such as 
pripionyl, acetyl, etc. 
The more preferred polyamines finding use within the scope of the present 
invention are polyalkylene polyamines, including alkylene diamine and 
substituted polyamines, e.g. alkyl and hyroxyalkyl-substituted 
polyalkylene polyamines. Preferably the alkylene groups contain from 2 to 
6 carbon atoms, there being preferably from 2 to 3 carbon atoms between 
the nitrogen atoms. Such groups are exemplified by ethyleneamines and 
including ethylene diamine, diethylene triamine, di(trimethylene) 
triamine, dipropylenetriamine, triethylenetetramine, etc. Such amines 
encompass isomers which are the branched-chain polyamines and the 
previously mentioned substituted polyamines, including hydroxy and 
hydrocarbyl-substituted polyamines. Among the polyalkylene polyamines, 
those containing 2 to 12 amine nitrogen atoms and 2 to 24 carbon atoms, 
are especially preferred and the C.sub.2 to C.sub.3 alkylene polyamines 
are most preferred, in particular, the lower polyalkylene polyamines, e.g. 
ethylene diamine, tetraethylenepentamine, etc. 
A Group II metal neutral or overbased hydrocarbyl sulfonate can be employed 
at from about 1 to 10 weight % relative to the alkylphenol, preferably 
from about 1 to 5 weight %. Where the product is intended as an additive 
for marine crankcase lubricated oil formulations the use of Group II metal 
neutral or overbased hydrocarbyl sulfonate is especially attractive 
because sulfonates are advantageously employed in such formulations in 
conjunction with the overbased sulfurized alkylphenates. 
Suitable Group II metal neutral or overbased hydrocarbyl sulfonates include 
natural or synthetic hydrocarbyl sulfonates such as petroleum sulfonate, 
synthetically alkylated aromatic sulfonates, or aliphatic sulfonates such 
as those derived from polyisobutylene. These sulfonates are well-known in 
the art. (Unlike phenates, "normal" sulfonates are neutral and hence are 
referred to as neutral sulfonates.) The hydrocarbyl group must have a 
sufficient number of carbon atoms to render the sulfonate molecule oil 
soluble. Preferably, the hydrocarbyl portion has at least 20 carbon atoms 
and may be aromatic or aliphatic, but is usually alkylaromatic. Most 
preferred for use are calcium, magnesium or barium sulfonates that are 
aromatic in character. Such sulfonates are conventionally used to 
facilitate the overbasing by keeping the calcium base in solutions. 
Sulfonates suitable for use in the present process are typically prepared 
by sulfonating a petroleum fraction having aromatic groups, usually mono- 
or dialkylbenzene groups, and then forming the metal salt of the sulfonic 
acid material. The sulfonates can optionally be overbased to yield 
products having Total Base Numbers up to about 400 or more by addition of 
an excess of a Group II metal hydroxide or oxide and optionally carbon 
dioxide. Calcium hydroxide or oxide is the most commonly used material to 
produce the basic overbased sulfonates. 
It is generally advantageous to use a small amount of an inert hydrocarbon 
diluent and solvent in the process to facilitate mixing and handling of 
the reaction mixture and product. Typically, a mineral oil will be used 
for this purpose because of its obvious compatibility with the use of the 
product in lubricating oil combinations. Suitable lubricating oil diluents 
which can be used include for example, solvent refined 100N, i.e., Cit-Con 
100N, and hydrotreated 100N, i.e., RLOP 100N, and the like. The inert 
hydrocarbon diluent preferably has a viscosity of from about 1 to about 20 
cSt at 100.degree. C. 
In the general preparation of overbased sulfurized alkylphenates, 
demulsifiers are frequently added to enhance the hydrolytic stability of 
the overbased sulfurized alkylphenate and may be similarly employed in the 
present process if desired. Suitable demulsifiers which can be used 
include, for example, nonionic detergents such as, for example, sold under 
the Trademark Triton X45 and Triton X-100 by Rohm and Haas (Philadelphia, 
Pa.) and ethoxylated p-octylphenols. Other suitable commercially available 
demulsifiers include Igepal CO-610 available from GAF Corporation (New 
York, N.Y.). Where used, demulsifiers are generally added at from 0.1 to 1 
weight % to the alkylphenol, preferably at from 0.1 to 0.5 weight %. 
LUBRICATING OIL COMPOSITIONS 
The oil-soluble, overbased sulfurized alkylphenate compositions produced by 
the process of this invention are useful lubricating oil additives 
imparting detergency and dispersancy properties to the lubricating oil as 
well as providing an alkalinity reserve in the oil. When employed in this 
manner, the amount of the oil-soluble, overbased sulfurized alkylphenate 
composition ranges from about 0.5 to 40 weight % of the total lubricant 
composition, although preferably from about 1 to 25 weight % of the total 
lubricant composition. Such lubricating oil compositions are useful in 
diesel engines, gasoline engines, as well as in marine engines. As noted 
above, when used in lubricating oil formulations for marine engines, such 
phenates are frequently used in combination with Group II metal overbased 
natural or synthetic hydrocarbyl sulfonates. 
Such lubricating oil compositions employ a finished lubricating oil, which 
may be single or multigrade. Multigrade lubricating oils are prepared by 
adding viscosity index (VI) improvers. Typical viscosity index improvers 
are polyalkyl methacrylates, ethylene, propylene copolymers, styrene-diene 
copolymers, and the like. So-called dispersant VI improvers, which exhibit 
dispersant properties as well as VI modifying properties, can also be used 
in such formulations. 
The lubricating oil, or base oil, used in such compositions may be mineral 
oil or synthetic oils of viscosity suitable for use in the crankcase of an 
internal combustion engine, such as gasoline engines and diesel engines, 
which include marine engines. Crankcase lubricating oils ordinarily have a 
viscosity of about 1300 cSt 0.degree. F. to 24 cSt at 210.degree. F. 
(99.degree. C.). The lubricating oils may be derived from synthetic or 
natural sources. Mineral oil for use as the base oil in this invention 
includes paraffinic, naphthenic and other oils that are ordinarily used in 
lubricating oil compositions. Synthetic oils include both hydrocarbon 
synthetic oils and synthetic esters. Useful synthetic hydrocarbon oils 
include liquid polymers of alpha olefins having the proper viscosity. 
Especially useful are the hydrogenated liquid oligomers of C.sub.6 to 
C.sub.12 alpha olefins such as 1-decene trimer. Likewise, alkyl benzenes 
of proper viscosity, such as didodecyl benzene, can be used. Useful 
synthetic esters include the esters of both monocarboxylic acid and 
polycarboxylic acids, as well as monohydroxy alkanols and polyols. Typical 
examples are didodecyl adipate, pentaerythritol tetracaproate, 
di-2-ethylhexyl adipate, dilaurylsebacate and the like. Complex esters 
prepared from mixtures of mono and dicarboxylic acid and mono and 
dihydroxy alkanols can also be used. 
Blends of hydrocarbon oils with synthetic oils are also useful. For 
example, blends of 10 to 25 weight % hydrogenated 1-decene trimer with 75 
to 90 weight % 150 SUS (100.degree. F.) mineral oil gives an excellent 
lubricating oil base. 
Other additives which may be present in the formulation include rust 
inhibitors, foam inhibitors, corrosion inhibitors, metal deactivators, 
pour point depressants, antioxidants, and a variety of other well-known 
additives.

EXAMPLES 
The invention will be further illustrated by following examples, which set 
forth particularly advantageous method embodiments. While the Examples are 
provided to illustrate the present invention, they are not intended to 
limit it. 
Neutralization Rate Test 
The Neutralization Rate Test (NRT) consists of recording the increase in pH 
of a continuously stirred heterogeneous mixture of aqueous acid and 
lubricating oil by means of a glass pH electrode as a function of time at 
25.degree. C. The results of the test are represented as the time 
necessary to reach an inflection point and/or a certain basic pH value 
(i.e., &gt;pH 7). The shorter the time to reach a basic pH value, the better 
the oil is at neutralizing acid. 
Example 1 
Preparation of an EDA Modified HOB Phenate From a Linear Alkyl Alkylphenol 
Into a 2 liter 5-neck round bottom flask was weighed 24.4 grams of a 
neutral sulfonate, 381.1 grams of a C.sub.20-28 linear alkyl-chain 
substituted alkylphenol, 239.1 grams of decyl alcohol, 103.4 grams of 
diluent oil (RLOP 100N available from Chevron) and 176.1 grams of lime. 
The flask was fitted with a reflux condenser, placed under a slight 
nitrogen purge, and the agitator turned on. The contents were then heated 
to 65.degree. C. over fifteen minutes. At 65.degree. C., 47.2 grams of 
solid sulfur was added to the flask and the temperature was held at 
65.degree. C. for thirty minutes. The reflux condenser was changed to a 
distillation configuration and the reaction temperature was then increased 
to 151.degree. C. over 35 minutes and held at 151.degree. C. for sixty 
minutes. Ten minutes into this sixty minute hold step, 21.8 grams of 
ethylene glycol was added to the reaction over thirty minutes. The 
temperature was then increased to 171.degree. C. over sixty minutes. At 
171.degree. C., the nitrogen purge was stopped and the addition of 84.8 
grams of ethylene glycol over 58 minutes was started simultaneously with 
the addition of 71 grams of carbon dioxide over 160 minutes. Ten minutes 
into this simultaneous addition of ethylene glycol and CO.sub.2, 47.6 
grams of ethylene diamine (EDA) was added over 95 minutes using an 
addition funnel. Following the addition of the CO.sub.2, the reaction was 
held at 171.degree. C. for twenty minutes and then the reaction was 
distilled by heating to 205.degree. C. over 35 minutes while reducing the 
vacuum on the system to 26 mm Hg. The temperature was held at 205.degree. 
C. for thirty minutes at 26 mm Hg vacuum. The reaction was then cooled to 
about 150.degree. C. and the vacuum released with nitrogen and 
approximately 25 ml of product was removed for crude sediment analysis 
(4.0 vol. %). The product was then diluted with approximately 300 ml of 
Chevron 225 thinner and filtered through a Buchner funnel with the aid of 
filter aid. 
The filtered product was distilled to remove the thinner to afford 284.8 
grams of final product having the following properties: TBN=333; Ca=1.2 
weight %; S=2.67 weight %; N=0.88 weight %; CO.sub.2 =8.8 weight %; 
Viscosity=203 cSt (100.degree. C.). 
Example 2 
Preparation of an EDA Modified HOB Phenate From a Branched Alkylphenol 
Into a 3 liter 5-neck round bottom flask was weighed 823.4 grams of dodecyl 
alkylphenol, 516.6 grams of diluent oil (RLOP 100N), 71.5 grams of a 
neutral sulfonate, and 0.2 grams of an antifoam agent (silicone oil) at 
atmospheric pressure. The flask was fitted with a distillation head and 
the agitator started. The contents of the flask were heated to 110.degree. 
C. over thirty minutes. When the reaction reached approximately 70.degree. 
C., 368 grams of lime were added. When the reaction reached 110.degree. 
C., 119 grams of solid sulfur were added and the vacuum was reduced to 
approximately 680 mm Hg. The reaction was then heated to 160.degree. C. 
over twenty minutes. When the reaction reached 160.degree. C., 100 grams 
of 2-ethylhexanol was added over approximately thirty minutes followed by 
148.9 grams of ethylene glycol which was added over sixty minutes. 
Following the addition of the ethylene glycol; the vacuum was increased to 
720 mm Hg, 228 grams of 2-ethyl-hexanol was added over sixty minutes and 
the temperature increased to 165.degree. C. over 75 minutes. The reaction 
temperature was held at 165.degree. C. and 720 mm Hg vacuum for 45 
minutes. The reaction flask was then brought to atmospheric pressure and: 
the temperature was increased to 170.degree. C. over 15 minutes; a mixture 
of 54 grams of ethylene diamine and 85.1 grams of ethylene glycol was 
added over 165 minutes and 108 grams of carbon dioxide was added according 
to the following rates: 0.74 grams/minute for 15 minutes; 0.97 
grams/minute for sixty minutes and finally 0.76 grams/minute for 51 
minutes. At the end of the CO.sub.2 addition, the reaction was distilled 
by increasing the temperature to 195.degree. C. over 45 minutes while the 
vacuum was gradually decreased to 40 mm Hg. When the reaction reached 
195.degree. C., it was held at 195.degree. C. and 40 mm Hg for one hour. 
The reaction was then cooled to approximately 160.degree. C. and the flask 
brought to atmospheric pressure with nitrogen gradually. When the reaction 
reached 160.degree. C., a 25 ml aliquout was removed for crude sediment 
analysis (1.6 vol. %). The reaction was filtered hot 
(150.degree.-160.degree. C.) through a pressure Buchner filter with the 
aid of nitrogen pressure (70-80 psi) and filter aid at a rate of 420 
kg/hour/m.sup.2. 
The filtered product had the following properties: TBN=293; Ca=9.69 weight 
%; S=3.71 weight %; N=0.76 weight %; CO.sub.2 =5.17 weight %; 
Viscosity=420 cSt (100.degree. C.). 
Example 3 
Preparation of an EDA Modified HOB Phenate from a Branched Alkylphenol 
The procedure of Example 2 was followed exactly except 150 grams of carbon 
dioxide was added using the following flow rates: 11 grams at 0.73 
grams/minutes then 52.5 grams at 0.88 grams/minute and finally 86.5 grams 
at 0.74 grams/minute. Following distillation of the reaction, an aliquout 
of the reaction was removed for crude sediment analysis (1.2 Vol. %). The 
filtered product had the following properties: TBN=299; Ca=9.66 weight %; 
S=3.69 weight %; N=0.86 weight %; CO.sub.2 =6.0 weight %; Viscosity=359 
cSt (100.degree. C.). 
Comparative Example A 
A commercially available metal overbased sulfurized dodecyl alkylphenol was 
used prepared from the same branched alkyl phenol used in Examples 2 and 
3, but not containing any polyamine. The Comparative Example A product 
typically has the following properties: TBN=250; Ca=9.25 weight %; S=3.37 
weight %; CO.sub.2 =5.0 weight %; Viscosity=350 cSt (100.degree. C.). 
Neutralization Rate Test Results 
The following Table summarizes results showing the improved sulfuric acid 
neutralization efficacy of two EDA modified HOB phenates compared to a 
non-EDA modified phenate in 70 BN oils. 
______________________________________ 
Time 
(sec) to 
Reach 
Detergent Tested 
Test Method pH 9 
______________________________________ 
Comparative Ex. A 
20 mls test oil and 40 ml 0.02 N H.sub.2 SO.sub.4 
1730 
Ex. 2 20 mls test oil and 40 ml 0.02 N H.sub.2 SO.sub.4 
1440 
Comparative Ex. A 
10 mls test oil and 50 ml 0.002 N H.sub.2 SO.sub.4 
340 
Ex. 2 10 mls test oil and 50 ml 0.002 N H.sub.2 SO.sub.4 
160 
Ex. 3 10 mls test oil and 50 ml 0.002 N H.sub.2 SO.sub.4 
303 
______________________________________ 
From the results shown in the above table, it is clear that the EDA 
modified metal overbased sulfurized alkylphenates show increased 
efficiency at neutralizing sulfuric acid, which is the main contribution 
to corrosive wear in slow speed crosshead diesel engines. Thus, when used 
in the formulation of marine cylinder lubricants (MCL's) it would be 
expected that these EDA modified metal overbased sulfurized alkylphenates 
will exhibit improved wear relative to metal overbased sulfurized 
alkylphenates not modified with polyamines. 
While the present invention has been described with reference to specific 
embodiments, this application 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.