Note: Descriptions are shown in the official language in which they were submitted.
1341 00 2
of -1-
HIGH TBN, LOW VISCOSITY, GROUP II METAL
OVERBASED SULFURIZED ALKYLPHENOLS
05
BA(:KGROUND OF THE INVENTION
1. Field o:E the Invention
The present invention is directed toward Group
II metal highly overbased sulfurized alkylphenols,
lubricating oil compositions containing these Group II
metal overb<~sed sulfurized alkylphenols as well as
lubricating oil concentrates containing these Group II
metal overbased sulfurized alkylphenols.
In particular, the present invention is directed
toward oil soluble, Group II metal overbased sulfurized
alkylphenols characterized as having a very high Total
Base Number (TBN), generally above about 300 TBN, and
viscosities of about 800 centistokes or less at 100°C.
The products of this invention are further characterized
as containing less than about 10$ of unsulfurized Group II
metal alkylphenol in the actives.
2. Pr for Art
Group II metal overbased sulfurized alkylphenols
are useful T~ubricating oil additives which impart
detergency <ind d.ispersancy properties to the lubricating
oil composition as well as providing for an alkalinity
reserve in i=he 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.
One method of preparing Group II metal overbased
sulfurized alkylphenols is described in U.S. Patent No.
3,178,368 where an alkylphenol, a sulfonate, a high
molecular weight alcohol, lubricating oil and sulfur are
combined anc9 heated with agitation. Hydrated lime is. then
added, the system heated and ethylene glycol added. Water
of reaction is removed, the mixture cooled, and carbon
dioxide added. Uncombined C02 is removed and the reaction
vessel is heated to remove ethylene glycol, water and the
1341002
O1 -2-
high molecular weight alcohol. The product is overbased
by the incorporation therein of hydrated lime and carbon
05 dioxide.
Such prior art methods provide for Group II
metal overbased su7Lfurized alkylphenols of approximately
250 TBN. Greater than 275 TBN Group II metal overbased
sulfurized a.lkylphenols of the prior art are too viscous
LO and require ineffic:i.ently large amounts of diluent in
order to be conveniently handled. See U.S. Patent No.
3,367,867. In order to overcome the problem of extremely
high viscosities ae:sociated with high TBN Group II metal
overbased sulfurized alkylphenols, U.S. Patent
15 No. 3,:367,867 discloses that the use of alkyl groups on
the alkylphenol which are mixtures of straight and
branched chain alkyl results in products having suitable
viscosities as wel7~ as antifoaming properties. Commercial
products encompassed by U.S. Patent No. 3,367,867 are
2U generally about 250 TBN.
While the process disclosed in U.S. Patent
No. 3,367,867 is u:>eful in preparing 250 TBN products of
acceptable viscosity, attempts to extend this technology
to prepare extremely high TBN Group II metal overbased
25 sulfurized alkylphenols, about 300 TBN and greater,
resulted in increae>ed viscosity as well as increasing
hydrolytic instability in the products. Accordingly,
there is a need to develop extremely high TBN Group II
metal overbased sulfurized alkylphenols of suitable
30 viscosity. It would be an additional advantage if such
high TBN Grcup II metal overbased sulfurized alkylphenols
of suitable viscosity were also hydrolytically stable.
I have now discovered novel Group II metal
overbased sulfuri.zed alkylphenols characterized as
3S possessing a Total Base Number of about 300 and greater
and having viscosit:ies of about 800 centistokes and less
at 100°C. The novel products of this invention are also
surprisingly hydro7Lytically stable.
The Group II metal overbased sulfurized
40 alkylphenols of t:hiLs invention are conveniently prepared
~~4~ooz
-3-
by employing a su:Ltable alkylphenol and a "sulfurization
catalyst" in the preparation of these additives. A
particularly preferred catalyst is 2-mercaptobenzothiazole
(MBT) and derivatives thereof.
To my knowledge, the use of a sulfurization catalyst
in the preparation of Group II metal overbased sulfurized
alkylphenols is not taught in the prior art. Prior art
references include U.S. Patent No. 4,100,085 which describes
the use of ammonia or ammonium hydroxide as a promoter in the
synthesis of overbased sulfurized alkylphenols. Likewise,
U.S. Patent No. 4,212,752 describes the use of certain amino
promoters, such as~ primary and secondary alkylamines,
polyalkyleneamine~., amino acids, etc. in the synthesis of
overbased sulfurized all~;ylphenols.
SUMMARY OF THE INVENTION
The present invention is directed toward low
viscosity, high THN, Group II metal overbased sulfurized
alkylphenols. In particular, in its composition aspect, the
present invention is directed toward oil-soluble, Group II
metal overbased sulfurized alkylphenols substantially free of
alkali metals characterized as possessing a Total Base Number
of from about 300 and greater, a viscosity of about 800
centistokes or less at 1.00°C and containing less than about
10% of unsulfurized Group II metal alkylphenols in the
actives.
The alkyl group of the alkylphenol contains a
sufficient number of carbon atoms to render the Group II metal
13411102
-3a-
overbased sulfuri.,ed all~.ylphenol oil soluble . In one
preferred embodiment, the alkyl group of said alkylphenol
contains from 25 t:o 100 mole percent predominantly straight
chain alkyl group: of from 15 to 35 carbon atoms and from 75
to 0 mole percent of thE~ alkyl groups are polypropenyl of from
9 to 18 carbon atoms. Pdore preferably, the alkyl group of
said alkylphenol contains from 35 to 100 mole percent
predominantly straight <:hain alkyl groups of from 15 to 35
carbon atoms and from 65 to 0 mole percent of the alkyl groups
are polypropenyl of
1341002
Ol -4-
from 9 to 1!3 carbon atoms. In yet another preferred
embodiment i:he alkyl group of said alkylphenol contains
OS from 40 to 'l0 mole percent predominantly straight chain
alkyl groups of from 15 to 35 carbon atoms and from 60 to
30 mole percent of the alkyl groups are polypropenyl of
from 9 to 18 carboin atoms. D1ost preferably, the alkyl
group of sa:Ld alkylphenol contains approximately 50 mole
percent predominantly straight chain alkyl groups of from
to 35 carbon atoms and approximately 50 mole percent of
the alkyl groups are polypropenyl of from 9 to 18 carbon
atoms.
Preferably, the Group II metal overbased
15 sulfurized alkylphfanols of this invention possess a Total
Base Number (TBN) of from about 300 to 400, more prefer-
ably from 37.5 to 400; even more preferably from 315 to
360; and moe~t preferably from 325 to 360.
Preferably, the Group II metal is selected from
2U the group consisting of calcium, magnesium, barium and
mixtures thereof. Most preferably, the Group II metal is
calcium.
The oil-soluble, Group II metal overbased
sulfurized alkylphenols of this invention are useful
lubricating oil adc9itives imparting detergency and
dispersancy properties to the lubricating oil as well as
providing an alkal:Lnity reserve in the oil. When employed
in this manr,.er, the amount of the oil-soluble, Group II
metal overba.sed su:lfurized alkylphenol ranges from about
0.5 to 40 weight percent of the total lubricant composi-
tion although prefer_abl.y from about 1 to 25 weight percent
of the total lubricant composition. Accordingly, another
aspect of this invention is a lubricating oil composition
comprising a.n oil of lubricating viscosity and from about
3S 0.5 to 40 weight percent of an oil-soluble, Group II metal
overbased sv.lfurized alkylphenol of this invention.
Lubricating oil connpositions of this invention are useful
in diesel engines, gasoline engines as well as in marine
engines. When emp:toyed in marine engines, the oil-
soluble, Group II rnetal overbased sulfurized alkylphenols
1 341 00 2
_5_
O1
are often used in c:onjunction with an oil-soluble Group II
metal overbased natural or synthetic hydrocarbyl
OS sulfonate. Therefore, still another aspect of this
invention is a lubricating oil composition comprising an
oil of lubricating viscosity and (a) from about 0.5 to 40
weight percent of an oil-soluble, Group II metal ove~rbased
sulfurized alkylphe nol of this invention; and (b) from
about 0.5 to 40 weight percent of an oil-soluble Group II
metal overbased nai:ural or synthetic hydrocarbyl
sulfonate.
As used herein, the term "Total Base Number" or
"TBN" refers to then amount of base equivalent to milli-
grams of KOH in 1. gram of sample. Thus, higher TBN
numbers reflect more alkaline products and therefore a
greater alkalinity reserve.
The term "hydrolytically stable" as used in
conjunction with Group II metal overbased sulfurized
alkylphenols means that compositions containing these
products will lose less than about 25~ of their Total Base
Number in a modified ASTPt D 2619 test. This test, as
modified, measures the hydrolytic stability of a product
by measuring its base loss upon exposure to moisture.
Greater base loss reflects poorer hydrolytic stability.
Hydrolytic stability of the Group II metal overbased
sulfurized alkylphe nols is an extremely important property
particularly in marine crankcase use where water exposure
is common. See van der Horst, Lubricant Engineering,
"Development of Modern Lubricants for Medium-Speed Marine
Diesel Engines" (1977); Thomas et al., "Modern C9arine
Diesel Engine Lubricants and their Development", Second
International Lubricant Symposium, Cairo, Egypt (1979).
In the process of preparing overbased sulfurized
alkylphenols, only the Group II metal sulfurized alkyl-
phenol is capable of being overbased. Accordingly, it is
desirable to maximize the amount of Group II metal
sulfurized alkylphe~nol in the reaction process. On the
other hand, unsulfurized alkylphenol can form a Group II
metal salt but this salt cannot be overbased by addition
1341002
Ol -6-
of Ca(OH)2 (and related materials) and carbon dioxide.
Accordingly, it is c9esirable to minimize the amount of
OS Group II metal unsulfurized alkylphenol in the reaction
process.
The term "actives" as applied to the
compositions of this invention refers to the Group hI
metal alkylphenol. and the Group II metal sulfurized
alkylphenol wherea:> the term "inactives" refers to
unreacted alkylphenol as well as any diluent oil contained
in the composition..
The amount of Group II metal sulfurized alkyl-
phenol as well as t:he amount of Group II metal alkylphenol
l5 contained in the actives can be determined by standard
analytical techniques. One technique employed herein
utilizes dialysis coupled with 1H-NMR.
As used herein, the term "predominantly straight
chain alkyl" means a predominantly linear alkyl group
which may contain ~>ome branching in the molecular
structure.
DETAILED DESCRIPTION OF THE INVENTION
The Group II metal overbased sulfurized alkyl-
phenols of this invention are prepared in processes
similar to those previously described in the art with the
exception that a sulfurization catalyst is also
employed. Prior art processes for preparing Group II
metal overbased sul.furized alkylphenols can provide
products having a 7.'otal Base Number as high as 300 or
more, some of which have acceptable viscosities but some
of these products are hydrolytically unstable. The
reasons for the inability of prior art processes to
consistently produce hydrolytically stable high TBN
overbased sulfurized alkylphenols is not readily apparent.
3S Upon careful examination of this problem and
without limitation to this theory, it appears that the
hydrolytic instability of high TBN products is due in part
to large amounts of: unsulfurized Group II metal alkyl-
phenol contained in the actives. It appears that this
incomplete sulfur incorporation is much more prevalent
1341pp2
_,_
o >l
when high molar ch<~rges of hydrated lime to alkylphenol
are used, i.e., greater than 2. That is to say, in the
OS process of E~reparing an overbased sulfurized alkylphenol,
hydrated lime, sulfur and alkylphenol are charged into a
reaction system. Sufficient sulfur is employed to convert
all of the a,lkylphemol to sulfurized alkylphenol. At a
molar charge of 2 or less of hydrated lime to alkylphenol,
the alkylphenol is generally converted to calcium
sulfurized alkylphe nol whereas at molar charges of greater
than 2, the product. contains large amounts of unsulfurized
calcium alkylpheno7L. On the other hand, molar charges of
hydrated lime to al_kylphenol of greater than 2 are
genera.Lly required to achieve 300+ TBN products. Thus,
the problem is readily apparent. With all other factors
held constant such as sulfur charge, C02 charge, etc., to
arrive at 300+ TBN products requires molar charges of
hydrated lime to al_kylphenol in excess of 2 which
invariably results in large amounts of unsulfurized
calcium alkylphenol which in turn reduces the TBN
incorporation because it cannot be overbased and tends to
increase the viscosity of the product. The incomplete
sulfurizati.on of the alkylphenol at high molar charges of
hydrated lime to al_kylphenol, i.e., >2, was heretofore
unrecognized and for which an explanation is not readily
available.
In any event, I have now discovered that the use
of a sulfurization catalyst in those processes employing
greater than 2 equivalents of hydrated lime or other
Group II metal oxide or hydroxide greatly enhances the
amount of Group I:I metal sulfurized alkylphenol in the
actives and greatly decreases the amount of unsulfurized
Group II metal alkylphenol in the actives. The high TBN
products of this invention are characterized by containing
at least about 90 mole percent and preferably at least 95
mole percent of Group II metal sulfurized alkylphenols in
the actives. In the converse, the products of this
invention by neces~>ity will contain at most about 10 mole
percent and prefer<~bly at most about 5 mole percent of the
1341002
_8-
unsulfurized Group II metal alkylphenols in the actives.
Because of the decrease in the amount of unsulfurized
05 Group II metal al.kylphenol in the actives, the higher TBN
products are possible. Moreover these products have
improved hydrolytic: stability as well as lower viscosity.
In accordance with this invention, it hasbeen
discovered that oil.-soluble, Group II metal overbased
sulfurized alkylphenols of this invention can be prepared
by reacting in lubricating oil appropriate amounts of a
sulfurization catalyst, sulfur, alkylphenol, a Group II
metal oxide, hydro};ide or C1-C6 alkoxide followed by
carbonation with C02. The reaction system will also
contain a C2-C4 alb;ylene glycol (such as 1,3-propylene
glycol, 1,4-butylene glycol, ethylene glycol, etc., but
preferably the C2-C:4 alkylene glycol is ethylene glycol),
a Group II metal overbased natural or synthetic
hydrocarbyl sulfonate and a high molecular weight
2U alcohol. The resulting products of this reaction are
termed by the art as a Group II metal overbased sulfurized
alkylphenols. The Group II metal overbased sulfurized
alkylphenols of this invention are characterized by
possessing a Total Base Number of about 300 or greater, a
viscosity of about 800 centistokes or less at 100°C and
containing about 10 mole percent or less of unsulfurized
Group II metal alkylphenol.
The sulfurization catalyst catalyzes the sulfur
incorporation onto the alkylphenol. Suitable sulfuriza-
tion catalysts include 2-mercaptobenzothiazole (P1BT) and
derivatives thereof' such as bis(2,2'-benzothiazolyl)
disulfide; 2(3H)-benzothiazolethione zinc salt; 2-benzo-
thiazolyl-N, N'-diethylthiocarbamyl sulfide; 4-morpholinyl-
2-benzothiazole disulfide; etc. Another suitable class of
sulfurization catalysts include dithiophosphates such as
zinc diisopropyl di.thiophosphate; zinc di-n-butyldithio-
phosphate) etc. Other suitable classes of sulfurization
catalysts include t:hioureas, thiurams, calcium polysulfide
and the like. Specific embodiments of these catalysts
1341002
Ol -9-
include N,N'-dibutylthiourea; ethylenethiourea; trimethyl-
thiourea, dipentamethylenethiuram disulfide, dipenta-
05 methylenethiourea tetrasulfide; dipentamethylenethiourea
hexasulfide; etc.
Th,e sul.furization catalyst is generally employed
at from about 0.5 1.0 10 weight percent to the alkylphenol
in the reaction sy:>tem and preferably at from about 1 to 2
weight percent. In a preferred embodiment, the sulfuriza-
tion catalyst is added to the reaction mixture as a
liquid. This can be accomplished by dissolving the
sulfurization catalyst in molten sulfur or in the
alkylpheno.l as a premix to the reaction.
l5 Sulfur is generally employed at from about 2 to
4 moles per mole o1. the alkylphenol in the reaction system
and preferably at from about 2 to 3 moles per mole of
alkylphenol. All. allotropic forms of sulfur can be
used. Alternatively, in place of sulfur, sulfur mono-
2U chloride may be employed. For the purposes of this
invention, sulfur monochloride is considered equivalent to
sulfur. The sulfur may be employed either as molten
sulfur or as a solid.
The Group II metal oxide, hydroxide or Cl-C6
25 alkoxide used to prepare the Group II metal alkylphenol
includes the oxide:a, hydroxides and alkoxides of calcium,
strontium, barium or magnesium. However, calcium, barium
and magnesium are preferred whereas calcium is most
preferred. The Croup II metal oxide, hydroxide, or C1-C6
30 alkoxide is employed at. a molar charge to the alkylphenol
of from greater than 2 to 4; although more preferably from
greater than 2 to .3.
Carbon dioxide is added to the reaction system
in conjunction with the Group II metal oxide, hydroxide or
3S C1-C6 alkoxide to form overbased products and is generally
employed from about. 1 to 3 moles per mole of alkylphenol,
although preferably from about 2 to 3 moles per mole of
alkylphenol charged to the reaction system.
The alkylphenol employed in this invention is
40 represented by the formula:
1341002
of -lo-
OH
05
. ~~~J I
R
wherein R is an alkyl group containing sufficient number
of carbon atoms to render the resulting Group II metal
overbased sulfurizE>c9 alkylphenol oil-soluble.
Preferab7Ly, R is alkyl wherein from about 25 to
100 mole percent of the alkyl group is predominantly
straight chain alkyl of from 15 to 35 carbon atoms and
from about 75 to 0 mole percent of the alkyl group is
polypropenyl of from 9 to 18 carbon atoms although more
preferably F; is alkyl wherein from about 35 to 100 mole
percent of the alkyl group is predominantly straight chain
2U of from 15 to 35 carbon atoms and from about 65 to 0 mole
percent of the alkyl group is polypropenyl of from 9 to 18
carbon atom;. Use of increasing amounts of predominantly
straight chain alkyl results in high TBN products
generally characterized by lower viscosities. On the
other hand, while polypropenylphenols are generally more
economical than predominantly straight chain alkylphenols,
use of greater than 75 mole percent polypropenylphenol in
the preparation of Group II metal overbased sulfurized
alkylphenol generally results in products of unacceptably
high viscosi.ties. However, use of a mixture of from 75
mole percent: or le:;s of polypropenylphenol of from 9 to 18
carbon atoms and from 25 mole percent or more of
predominantly straight chain alkylphenol of from 15 to 35
carbon atoms allow:a for more economical products of
acceptable viscosities.
The alkylphenols of Formula I above are prepared
by reacting the appropriate olefin or olefin mixture with
phenol in the presence of an alkylating catalyst at a
temperature of from about 60°C to 200°C, and preferably
125°C to 180°C either neat or in an essentially inert
1341 pp2
-11-
ol
solvent at a,tmosphe:ric pressure. A preferred alkylating
catalyst is a sulfonic acid catalyst such as Amberlyst 15~
OS available from Rohrn and Haas, Philadelphia, Pennsylvania.
Molar ratio of rea<:tants may be used. Alternatively,
molar excess; of phenol can be employed, i.e., 2-2.5
equivalents of phenol for each equivalent of olefinwith
unreacted phenol recycled. The latter process maximizes
LO monoalkylphenol. hxamples of inert solvents include
benzene, toluene, c:hlorobenzene and 250 thinner which is a
mixture of aromatics, paraffins and naphthenes.
The alky:Lphenols employed in this invention are
either ortho alkylp henols of the formula:
OH
R
°J I I
2U
or para-alkylpheno:Ls of the formula:
OH
III
R
Preferably, R is predominantly para with no more than
about 50 mole percent of the R alkyl group being in the
ortho position; anc9 more preferably no more than about 35
mole percent. of thc~ alkyl group being in the ortho
position. 7a is be=:Lieved that p-alkylphenols, III,
3S facilitate the preparation of highly overbased Group II
metal sulfurized a:Lkylphenols. Accordingly, it is
desirable tc> employ an olefin which results in maximum
para alkylphenol content in the alkylphenol. In this
regard, while polypropene generally adds in the para
position, o:~,efins ~~ontaining no branching will add at both
1341002
-12-
01
the ortho or para position. One method of enhancing the
para content of the alkylphenol prepared from straight
05 chain olefins is by use of a predominantly straight chain
olefin fractions containing some branching in the
molecular structure at the double bond such as structures
IV and V
Rl R1
jC= CH2 R3CH= \
R2 R2
IV V
(vinylidine) (trisubstituted vinyl)
1S
wherein Rl, R2 and R3 form the remainder of the olefin.
While being predomiW antly straight chain, the branched
portion of the molecular structure allows for formation of
a tertiary carbonium ion during the alkylation process.
2U Without being limited to any theory, it is believed that
the steric hindrance associated with a tertiary carbonium
ion inhibits ortho alkylation and thereby results in
enhanced para subst:itution. Suitable predominantly
straight chain olefins are those wherein about 75 to 100
25 number percent and preferably about 85 to 100 number
percent of the indilvidual carbon atoms of the olefin are
either primary (CH=;-) or secondary (-CH2-). Included in
the terms primary or secondary are alpha olefins (-CH=CH2)
and internal olefins (-CH=CH-). In the converse, such
30 predominantly straight chain olefins can contain from 0 to
about 25 number percent although preferably from 0 to
about 15 number percent of tertiary carbon atoms.
Included within the term tertiary are trisubstituted vinyl
groups (:C=C'H-) anti vinyl idine (,C=CH2) .
3S Predominantly straight chain olefin fractions
are commercially available products such as C18-C30
olefins, available from Ethyl Corporation, Baton Rouge,
Louisiana. These olefins are predominantly straight chain
in that from 80 to 100 number percent of the carbon atoms
40 in the olefins are either primary or secondary. On the
~ 34~ o0 2
-13-
01
other hand, about 40 mole percent of the olefins contained
in the olefin fraction are branched olefins. That is to
05 say while being otherwise predominantly straight chain 40
mole percent of al7L of the olefins are branched in the
form of tri~~ubstituted vinyl or vinylidine structure.
Likewise, C24-C28 olefin fractions, available from Chevron
Chemical Corporation, San Francisco, CA, are also
predominantly straight-chain but contain about 40 mole
percent or more br<~nched olefin, containing predominantly
vinylidine olefin. Straight chain olefins, containing
less than at~out 5 rnole percent branched olefins, are
available from She7L1 Chemical Company, Houston, Texas.
This is i~he appropriate time to distinguish
between "predominantly straight-chain olefins containing
80 to 100 number pEarcent of either primary or secondary
carbon atom. in the olefin" and a "predominantly straight-
chain olefin fraction wherein about 40 mole percent of the
2U olefins are branch<~d". In the first case, the olefin is
viewed on a molecu:Lar basis and requires that at least 80
number percent of the carbon atoms be primary or
secondary. In thia case, a branched olefin such as
trisubstituted vinyl or vinylidine is nonetheless
predominantly straight-chain if a sufficient number of the
remaining carbon atoms are primary or secondary such that
at least 80 number percent of the carbon atoms in this
olefin are primary or secondary.
On the other hand, a predominantly straight-
chain olefin fraction wherein about 40 mole percent of the
olefins are branched as is viewed from a composition
basis. That: is this predominantly straight-chain olefin
fraction car> -contain olefins such as alpha olefins,
internal olefins, trisubstituted vinyl and vinylidine.
When viewinct the entire predominantly straight-chain
olefin fraction, 40 mole percent of the olefins are
branched, i.e., either trisubstituted vinyl or vinylidine,
whereas the remainder are either alpha olefins or internal
olefins.
1341002
O1 -14-
The reaction to prepare the Group II metal
overbased sulfurized alkylphenols of this invention also
OS employs an alkylene glycol, i.e., ethylene glycol, a high
molecular weight alcohol (generally decyl alcohol) and a
Group II metal overbased natural or synthetic hydrocarbyl
sulfonate.
The ethylene glycol is generally employed at a
molar charge to the alkylphenol of about 1 to 4, although
preferably tizis molar charge is from about 2 to 3.
Alternativel~l, 2-ethylhexanol may be employed in
conjunction with ethylene glycol at weight ratios such as
80~ by weighs: 2-ethylhexanol and 20$ by weight ethylene
glycol.
The preferred high molecular weight alcohol is
decyl alcohol. which is employed at a molar charge to the
alkylphenol from about 0.5 to 4, although preferably from
about 1 to 2.
10 The Group II metal overbased natural or
synthetic hydrocarbyl sulfonates may be either petroleum
sulfonate, sy~nthetir_ally alkylated aromatic sulfonates, or
aliphatic sul.fonatea such as those derived from poly-
isobutylene. These sulfonates are well-known in the
art. The hyclrocarb~yl 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 atc>ms and may be aromatic or aliphatic, but is
usually alkyl.aromatic. Most preferred for use are
calcium, magnesium or barium sulfonates which are aromatic
in character.
Certain sulfonates are typically prepared by
sulfonating ~~ petro:Leum fraction having aromatic groups,
usually mono-~ or c9ialkylbenzene groups, and then forming
40
1341002
O1 -15-
the metal salt of the sulfonic acid material. Other feed-
stocks used I:or pre paring these sulfonates include
05 syntheticall~~ alkylated benzenes and aliphatic hydro-
carbons prepared by polymerizing a mono- or diolefin, for
example, a polyisobutenyl group prepared by polymerizing
isobutene. The metallic salts are formed directly or. by
metathesis u:;ing we_L1-known procedures.
They sulfonates are then overbased to yield
products having Total Hase Numbers up to about 400 or more
by addition of carbon dioxide and a Group II metal
hydroxide or oxide. Calcium hydroxide or oxide is the
most commonly used rnaterial to produce the basic overbased
sulfonates. These materials are well-known in the art.
The Group II metal overbased natural. or
synthetic hydrocar.byl sulfonate is employed at from about
1 to 20 weight perceant to the alkylphenol, although pref-
erably from about 1 to 10 weight percent. The Group II
metal overba~;ed natural or synthetic hydrocarbyl sulfonate
described above are also employed in lubricating oil
formulations in conjunction with the Group II metal
overbased sul.furize<9 alkylphenols; especially in marine
crankcase formulations.
Alt:ernativ ely, in lieu of a Group II metal
overbased natural or synthetic hydrocarbyl sulfonate, an
alkenyl succ9.nimide may be employed. Alkenyl succinimides
are well-known in the art. The alkenyl succinimides are
the reaction product of a polyolefin polymer-substituted
l0 succinic anhydride with an amine,. preferably a poly-
alkylene polyamine. The polyolefin polymer-substituted
succinic anhydrides are obtained by reaction of a poly-
olefin polymer or a derivative thereof with malefic
anhydride. The succinic anhydride thus obtained is
3S reacted with the amine compound. The preparation of the
alkenyl succi.nimidea has been described many times in the
art. See, for example, U.S. Patent Nos. 3,390,082;
3,219,666; and 3,172,892, ' Reduction of the alkenyl
substituted succi~aic anhydride yields the
1341 pp 2
O1 -16-
corresponding alkyl derivative. The alkyl succinimides
are intende<9 to be included within the scope of the term
05 "alkenyl suc:cinimide". A product comprising predominantly
mono- or bis-succinimide can be prepared by controlling
the,molar ratios of the reactants. Thus, for example, if
one mole or amine is reacted with one mole of the al~kenyl
or alkyl substituted succinic anhydride, a predominantly
LO mono-succin:imide product will be prepared. If two moles
of the succinic anhydride are reacted per mole of poly-
amine, a bis-succi;nimic9e will be prepared.
The po:Lyisobutene from which the polyisobutene-
substituted succ:inic anhydride is obtained by polymerizing
15 isobutene can vary widely in its compositions. The
average number of carbon atoms can range from 30 or less
to 250 or more, with a resulting number average molecular
weight of about X00 or less to 3,000 or more. Preferably,
the average number of carbon atoms per polyisobutene mole-
2U cule will range from about 50 to about 100 with the poly-
isobutenes Having a number average molecular weight of
about 600 to about 1,500. More preferably, the average
number of carbon atoms are polyisobutene molecule ranges
from about E.0 to about 90, and the number average
25 molecular weight ranges from about 800 to 1,300. The
polyisobutene is reacted with malefic anhydride according
to well-known procedures to yield the polyisobutene-
substituted succin:ic anhydride.
In preparing the alkenyl succinimide, the
30 substituted succin:ic anhydride is reacted with a poly-
alkylene pol.yamine to yield the corresponding
succinimide. Each alkylene radical of the polyalkylene
polyamine a=,ually has up to about 8 carbon atoms. The
number of alkylene radicals can range up to about 8. The
35 alkylene radical is exemplified by ethylene, propylene,
butylene, trimethylene, tetramethylene, pentamethylene,
hexamethylene, octamethylene, etc. The number of amino
groups generally, but not necessarily, is one greater than
the number of alky7lene radicals present in the amine,
40 i.e., if a polyal.kylene polyamine contains 3 alkylene
1341 p~ 2
-17-
Oi
radicals, ii. will usually contain 4 amino radicals. The
number of amino radicals can range up to about 9.
05 Preferably, the alkylene radical contains from about 2 to
about 4 carbon atoms and all amine groups are primary or
secondary. In this case, the number of amine groups
exceeds the number of alkylene groups by 1. Preferably,
the polyalkylene polyamine contains from 3 to 5 amine
groups. Specific: examples of the polyalkylene polyamines
include eth~~leneciiamine, diethylenetriamine, triethylene-
tetramine, propylenediamine, tripropylenetetramine,
tetraethylenepentamine, trimethylenediamine, penta-
ethylenehexamine, c9i-(trimethylene)triamine,
tri(hexamethylene)tetramine, etc.
When emp:Loyed the amount of alkenyl succinimide
used is from about 1 to 20 weight percent to the alkyl-
phenol, although preferably from about 1 to 10 weight
percent.
10 The reaci~ion to prepare the Group II metal
overbased sulfurized alkylphenols of this invention is
conducted by adding at the appropriate ratios the alkyl-
phenol, the Group .CI metal overbased natural or synthetic
hydrocarbyl sulfon<~te, the high molecular weight alcohol,
and the sulfurization catalyst. The reaction is generally
conducted ir. an inE>rt diluent such as lubricating oil.
Suitable lubricating oil diluent include solvent refined
100N, i.e., Cit Con 100N;~and hydrotreated 100N, i.e. RLOP
100N. After combination of the above, the system is
heated to between 90°C and 155°C with agitation and sulfur
as well as the Group II metal oxide, hydroxide or C1-C6
alkoxide is added f-_allowed by addition of the ethylene
glycol. Water of reaction is removed, the mixture heated
to about 175°C, and carbon dioxide added. Afterwards, any
3S uncombined carbon dioxide is removed and the reaction
system heated to remove ethylene glycol, water and the
high molecular weight alcohol to yield a composition
termed by the art: as a Group II metal overbased sulfurized
alkylphenol.
~E- Trar/.,~ -Mc~ r~;
1341 pp2
of -1$-
In a preferred embodiment, it has been found
that the ad<9ition of a demulsifier such as Triton X-45 and
05 Triton X-100 may synergistically enhance the hydrolytic
stability of the Group II metal overbased sulfurized
alkylphenol" Triton X-45 and Triton X-100 are nonionic
detergents useful as demulsifiers and are available~from
Rohm and Haas, Philadelphia, PA. These demulsifiers are
ethoxylated p-octylphenols. Other suitable demulsifiers
include Igepal CO-610 available from GAF Corporation, New
York, NY. :_n one preferred embodiment, the demulsifier
and sulfuri~;ation catalyst is combined. That is the
aqueous solution contains calcium polysulfide and Triton
X-100. Such a pro<9uct is sold by Chevron Chemical
Company, San Francisco, CA, under the trade name of
ORTHORIX~. Demulsifiers are generally added at from 0.1
to 1 weight perceni~ to the alkylphenol, preferably at from
0. 1 to 0. 5 we fight percent.
2U The lubricating oil compositions of this
invention employ a finished lubricating oil which may be
single or mu.ltigrade, t4ultigrade lubricating oils are
prepared by adding viscosity index (VI) improvers.
Typical viscosity :index improvers are polyalkyl meth-
acrylates, ethylene', propylene copolymers, styrene-diene
copolymers and the like. So-called decorated VI improvers
having both viscosity index and dispersant properties are
also suitable for use in the formulations of this
invention.
The lubricating oil used in the compositions of
this invention may be mineral oil or synthetic oils of
viscosity suitable for use in the crankcase of an internal
combustion engine ~>uch as gasoline engines and diesel
engines which include marine engines. Crankcase
3S lubricating oils ordinarily have a viscosity of about 1300
cst 0°F to 24 cst at 210°F (99°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
~- Traoj.~- Ma r~r
1341002
O1 -19-
include both hydrocarbon synthetic oils and synthetic
esters. Useful synthetic hydrocarbon oils include liquid
05 polymers of alpha-olefins having the proper viscosity.
Especially useful are the hydrogenated liquid oligomers of
~6 to 12 alpha-ol.ef:ins 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 mono-carboxylic acid and polycarboxylic
acids as well as mono-hydroxy alkanols and polyols.
Typical examples are didodecyl adipate, pentaerythritol
tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate
and the like. Camplex esters prepared from mixtures of
mono and dicarboxyl.ic acid and mono and dihydroxy alkanols
can also be used.
Blends of: hydrocarbon oils with synthetic oils
are also useful. E'or example, blends of 10 to 25 weight
percent hydrogenated 1-decene trimer with 75 to 90 weight
percent 150 SUS (100°F) mineral oil gives an excellent
lubricating oil ba~;e.
Lubricating oil additive concentrates are also
included within they scope of this invention. The
concentrate form comprises from about 60 to 20 weight
percent of an oil of lubricating viscosity and from about
40 to 80 weight percent of an oil soluble, hydrolytically
stable Group II metal overbased sulfurized alkylphenol of
this invention.
Other additives which may be present in the
formulation includes rust inhibitors, foam inhibitors,
corrosion inhibitors, metal deactivators, pour point
depressants, antio~;idants, and a variety of other well-
known additives.
The following examples are offered to
specifically illustrate the invention. These examples and
illustrations are not to be construed in any way as
limiting the scope of the invention.
It is noted that two titrimeters were employed
to measure the TBN of some of the examples herein. The
TBN's reported herein were obtained from either
~3~~002
O1 -20-
titrimeter. The 7.'BN's obtained from these two titrimeters
were within 3-5$ of each other. It is understood that the
05 TBN values reported herein are believed to be accurate at
t5~. TBN'a obtained from both titrimeters are reported
for some of the examples.
EXAhIPLES
Example 1
Preparation of a C18-C30 Alkylphenol
To a 2-liter flask, equipped with stirrer, Dean
Stark trap, condensor and nitrogen inlet and outlet was
added 857 gms of a predominantly Clg to C30 olefin mixture
(olefin content: C16-0.5$; C18-6.6; C20-26.2$; C22-27.7$;
C24-18.2; C26-9.0~; C28-4.5~; C30-28;x; greater than
C30-4.5~) wherein in the entire olefin fraction, at least
30 mole percent of said olefins contain trisubstituted
vinyl groups (available from Ethyl Corporation, Baton
Rouge, LA), 720 gm.s phenol, 55 gms of a sulfonic acid
2U
cation exchange resin (polystyrene crosslinked with
divinylbenzene) catalyst (Amberlyst 15~ available from
Rohm and Haas, Philadelphia, Pennsylvania). The reaction
mixture was heated to about 145°C for about 6 hours with
stirring under a nitrogen atmosphere. The reaction
mixture was stripped by heating under vacuum and the
resulting product filtered hot over diatomaceous earth to
afford 947 gms of a C18-C30 alkylphenol with a hydroxyl
number. of 118 and 56~ para-alkylphenol content.
Example 2
Preparation of a C20-C28 Alkylphenol
To a 2-liter flask, equipped with stirrer, Dean
Stark trap, condensor and nitrogen inlet and outlet was
added 674 gms of a predominantly C20 to C28 olefin mixture
(olefin content: C18-2$; C20-280; C22-19~; C24-13~;
C26-21~; C28-11~; and greater than C30-6~) wherein in the
entire olefin fraction at least 20 mole percent of said
olefins contain vinylidine groups (C20-C24 olefins and
C24-C28 olefins are available from Chevron Chemical
Company, San Francisco, CA and are then physically mixed
1 341 pa z
Ol -21-
at an equal mole basis to provide a C20-C28 olefin
mixture), 211.5 grams of phenol, 43 grams of a sulfonic
OS acid cation exchange resin (polystyrene crosslinked with
divinylbenzene) catalyst (Amberlyst 15~ available from
Rohm and Haas, Phi_'Ladelphia, PA). The reaction mixture
was heated to about. 140°C for about 8 hours with stirring
under a nitrogen ai=mosphere. The reaction mixture was
stripped by heati.nq under vacuum and the product was
filtered hot over diatomaceous earth to afford 574 grams
of a C20-C28 alkylp henol with a hydroxyl number of 110 and
with 56~ para-alkylphenol content.
Example 3
Preparation of Tetrapropenylphenol
To a 2-liter flask, equipped with stirrer, Dean-
Stark trap, condensor, and nitrogen inlet and outlet was '
added 567 grams of tetrapropylene, 540 grams of phenol, 72
grams of a sulfonic acid cation exchange resin (polystyrene
crosslinked with di.vinylbenzene) catalyst (Amberlyst 15~
available from Rohm and Haas, Philadelphia, PA). The
reaction mixture was heated to about 110°C for about 3
hours with stirring under a nitrogen atmosphere. The
reaction mixture was stripped by heating under vacuum and
the resulting product filtered hot over diatomaceous earth
to afford 626 grams of tetrapropenylphenol and with a
hydroxyl number of 205 and with 96$ para-alkylphenol
content.
Example 4
Into a 0.5-liter 3 neck-flask, equipped with
stirrer, Dean-Stark trap, condensor, and nitrogen inlet
and outlet was charged 100 grams of phenol. The system
was heated to 55°C and then charged with 55 grams of
C24 C28 olefin, available from Chevron Chemical Company,
San Francisco, CA, and 12.5 grams of Filtrol-13, an acid
activated clay available from Filtrol Corporation,
Los Angeles, CA. P,fterwards, 130.5 grams of C18-C30
olefin, available from Ethyl Corp., Baton Rouge, LA, was
added over 1 hour while heating the system from between
135°C to 145°C. The reaction was stopped and filtered.
~YC1 ~.~ - ~rJA ~~
1341002'
O1 -22-
The filtered produce was transferred to a clean flask,
placed under vacuum (~50 mm Hg) and heated to 215°C with a
OS small nitrogen sweep. The nitrogen was shut off and the
vacuum (~50 mm Hg) continued at 215°C for 30 minutes to
yield an al~;ylphenol having a hydroxyl number of 106.
Example 5 '
Preparation of Calcium Overbased
Hydrocarbyl Sulfonate
A. Preparation of Sodium Hydrocarbyl Sulfonate
Into a rc~acti.on vessel is charged 646 grams of
feedstock (solvent refined 500N lubricating oil which is a
mixture of alkyl aromatics, naphthenes and paraffins). At
75°F, 150.8 grams of oleum ( ~27. 6~ S03) is charged to the
reaction ve=_;sel over a 10 minute addition period. The
reaction temperature is allowed to rise - generally to
about 100°F. Afterwards, 12.3 ml of water as well as
540 ml of Cr~evror~ 265~thinner, which is a mixture of
2U aromatics, naphthenes and paraffins, is added to the
system. The systenn is maintained at 150°F for 1 hour. At
this time, 1.25 ml of an aqueous solution containing 25~ by
weight sodium hydroxide is added to the system. The
reaction is maint:a:ined at 150°F for 1 hour. After
settling, the aqueous layer is removed and the organic
solution then is maintained for at least 1 hour. After
' this period, any a<9ditional aqueous layer which had
settled out is also removed. The system is stripped at
350°F, atmoe;pheric pressure with an air sweep to yield the
sodium hydrocarbyl sulfonate which is purified as
follows: The sodium hydrocarbyl sulfonate is dissolved in
330 ml of a~:ueous secondary butyl alcohol. 160 ml of an
aqueous solution containing 4~ by weight sodium chloride
is added to the system. The system is heated to 150°F and
maintained at 150°f? for 2 hours. After settling, brine is
removed. An addi.t:ional 80 ml of an aqueous solution
containing 5.$ by wfaight sodium chloride is added to the
system. The system is heated to 150°F and maintained at
150°F for 1 hour. After settling, brine is removed.
220 ml of water is added to the system and the system
~ ~rao%_ /~1uYI~
134~~~z
Ol -23-
heated to 1~~0°F. 'Che system is maintained at 150°F for 1
hour. Afterwards, water and unsulfonated oil layer is
05 removed leaving the aqueous secondary butyl alcohol
solution containing the sodium hydrocarbyl sulfonate.
B. Pre aratio n of Calcium Hydrocarbyl Sulfonate
To the ac;ueous secondary butyl alcohol solution
containing the sodium hydrocarbyl sulfonate, produced as
in A above, is added 550 ml of a solution containing
water, secondary butyl alcohol and calcium chloride (~lOb
CaCl2). The system is heated to 150°F and is maintained
at 150°F for 1 hour. After settling, brine is removed.
340 ml of water and 170 ml of an aqueous solution
15 containing 90~ by weight calcium chloride is added to the
system. The system is heated to 150°F and is maintained
at 150°F for at least 1 hour. After settling, brine is
removed. 340 ml of water and 170 ml of an aqueous
solution containing 40~ by weight calcium chloride is
2U added to the system. The system is heated to 150°F and is
maintained at 150°F' for at least 1 hour. After settling,
brine is removed. 340 ml of water is added to the
system. The system is heated to 150°F and is maintained
at 150°F for 1 hour'. After settling, the aqueous layer is
25 removed. An additional 340 ml of water is then added to
the system. The system is heated to 150°F and is
maintained at 150°f for 1 hour. After settling, the
aqueous layer is removed. The aqueous secondary butyl
alcohol solution ie; then stripped at elevated temperatures
30 and reduced pressures to yield calcium hydrocarbyl
sulfonate.
C. Preparation of Calcium Overbased
Hydrocarbyl Sulfonate
Into a 5C10 ml 3-neck round bottom flask equipped
35 with a mechanical ~~tirrer, is added sufficient diluent oil
to the calcium hydrocarbyl sulfonate, produced above, to
yield 270 grams of a composition at 1.65 by weight
calcium. 42.4 grams water and 10.8 grams calcium
hydroxide are added to the system. A reflux condensor is
40 attached to one side neck and a thermometer is attached to
134~~~?
O1 -24-
the other side neck of the 3-neck round bottom flask. The
system is heated to reflux 0210°F) and held there for at
OS least 1 hour. The reaction system is then distilled by
heating to a bottorns temperature of 330°F/atmospheric
pressure. P,fterwards, the temperature is raised to 400°F
under vacuum. (~20 non Hg). The system is then cooled, to
300°F and the vacuum is discontinued. 20 grams of
diatomaceous earth is added to the product and the product
filtered through a 1/4 inch diatomaceous earth pad on a
Buchner funnel, which is preheated prior to filtration to
yield the title compound which is generally of
approximately 16 Total Base Number.
Example 6
Preparation of 340 TBN Calcium
Overbased Sulfurized Alkylphenol
Into a 2-liter, 4-neck flask was charged
196 grams of tetrapropenylphenol, prepared in a manner
2U similar to Example 3, 354 grams of C18-C30 alkylphenol,
prepared in a manner similar to Example 1, 410 grams of
decyl alcohol, 20 grams of 2-mercaptobenzothiazole,
40 grams of a calcium overbased hydrocarbyl sulfonate,
prepared in a manner similar to Example 5 and 200 grams of
Cit-Con 100N oil. The system was heated with agitation at
90°C at which time 296 grams of Ca(OH)2 and 108 grams of
sulfur were charged to the reaction system. The reaction
system was then held at 90°C for_ 45 minutes. Afterwards,
the reaction temperature was raised over a 15 minute
period to 150°C whereupon 206 grams ethylene glycol was
added over a 60 minute period via an addition funnel.
After complete addition of ethylene glycol, the reaction
temperature was increased to 160°C over a 15 minute period
and held at this temperature for 1 hour. At this time,
the stirring rate of the reaction mixture was increased to
moderately fast, and the reaction temperature was then
increased at a rate of 5°C per 20 minutes until the
reaction temperature reached 175°C whereupon 144 grams of
carbon dioxi~9e was charged through a flowmeter to the
reaction system over a three hour period. The reaction
1341 002
O1 -25-
temperature was the n increased to 195°C and the system
stripped under vacuum (~10 mm of Hg) for a period of 30
05 minutes to ~~ield 1:269 grams of product which was purified
by addition of 3 weight percent diatomaceous earth
at ,~t-
consisting of 50~ Hi-Flo, and 50$ of 512 Celite,
commercial diatomaceous earth products available from
Manville, Filtration and Minerals Division, Denver, CO,
followed by filtrai_ion through a 1/4 inch Celite pad on a
Buchner funnel. The resulting product has a Total Base
Number of 39.0 (324 on second titrimeter); a viscosity of
720 centistokes at 100°C; a sulfur content of 4.4 weight
percent; and a cal<:ium content of 12.3 weight percent.
Example 7
Prepay-ation of a 343 TBN Calcium
Overbased Sulfurized Alkylphenol
Into a 10 gallon stainless steel reactor was
charged 3.53 kilograms of tetrapropenylphenol, prepared in
2U a manner similar to Example 3, 6.73 kilograms of C18-C30
alkylphenol, prepared in a manner similar to Example 1,
7.6 kilograms of decyl alcohol, 380 grams of 2-mercapto-
benzothiazole, 760 grams of a calcium overbased
hydrocarbyl sulfonate, prepared in a manner similar to
Example 5 and 3.8 kilograms of Cit-Con 100N oil. The
system was heated with agitation to 90°C at which time '
5.62 kilograms of C:a(OH)2 and 2.05 kilograms sulfur were
chargec9 to the reaction system. The reaction system was
then held at 90°C f:or 45 minutes. Afterwards, the
reaction temperature was raised over a 15 minute period to
150°C whereupon 3.°.~1 kilograms ethylene glycol was added
over a 60 minute period via an addition flask. After
complete addition of ethylene glycol, the reaction
temperature was increased to 160°C and held at this
3S temperature for 1 hour. At this time, the stirring rate
of the reaction mixture was increased and the reaction .
temperature was then increased at a rate of 5°C per 20
minutes until the reaction temperature reached 175°C
whereupon 2.74 kilograms of C02 was charged to the
reaction system over a three hour period. The reaction
~ T r ~.e -- ha ~-Ir
1341002
O1 -26-
temperature was then increased to 195°C and the system
stripped under vacuum (~10 mm of FFg) for a period of 30
05 minutes. The system was cooled overnight and then heated
and agitated. The product was then purified by addition
of 3 weight percent: diatomaceous earth consisting of. 50$
Hi-Flo, and 50$ of 512 Celite, commercial diatomaceous
earth products available from P9anville, Filtration and
LO Minerals Division, Denver, CO, followed by filtration to
yield a product having a Total Base Number of 343 (324 on
second titrimeter); a viscosity of 463 centistokes at
100°C; a sulfur content of 4.4 weight percent, a calcium
content of 12.4 weight percent and 1.6$ crude sediment.
15 Example 8
Into a 1-liter, 4-neck flask was added 99 grams
of tetrapropenylphenol, prepared in a manner similar to
Example 3 , 167 grams of a C20-C28 alkylphenol, prepared in
a manner similar to Example 2, 210 grams of decyl alcohol,
2U 10 grams of 2-mercaptobenzothiazole, 20 grams of a calcium
overbased hydrocarbyl sulfonate, prepared in a manner
similar to Example 5 and 100 grams of Cit-Con 100N oil.
The system was heated with agitation to 90°C at which time
148 grams of Ca(OH)2 and 56 grams of sublimed sulfur were
25 Charged to the reaction system. The reaction was then
held at 90°C for 4-'. minutes. Afterwards, the reaction
temperature was raised over a 15 minute period to 150°C
whereupon 103 grams of ethylene glycol was added over a 60
minute period. After complete addition of the ethylene
30 glycol, the reaction temperature was increased to 160°C
and held at this temperature for 1 hour. At this time,
the reaction temperature was increased at a rate of 5°C
per 20 minutes until the reaction temperature reached
175°C whereupon 72 grams of carbon dioxide was charged to
35 the reaction system over a three hour period. The
reaction temperature was then increased to 195°C and the
system stripped under vacuum (~10 mm of Hg) for a period
of 30 minutes. Secfiment was removed and 800 ml of 250
thinner which is a mixture of aromatics, paraffins and
40 naphthenes was added to the system as well as 3 weight
134 ~~Z
O1 -27-
percent diatomaceous earth consisting of 50$ Hi-Flo and
50~ of 512 C'.elite, commercial diatomaceous earth products
OS available from Manville, Filtration and Minerals Division,
Denver, C0. The system was filtered through a 1/4 inch
Celite pad on a Buc:hner funnel. Afterwards, the thinner
was removed by striipping at elevated temperatures and
reduced pressures i.o yield 581 grams of a calcium
10 overbased sulfurized alkylphenol having a Total Base
Number of 328 (obtained from second titrimeter) a
viscosity of 365 centistokes at 100°C; a sulfur content of
3.96 weight percent:; and a calcium content of 12.3 weight
percent.
15 Example 9
Into a 1-liter, 4-neck flask was added 99 grams
of tetrapropenylphe~nol, prepared in a manner similar to
Example 3, 167 grams of a C20-C28 alkylphenol, prepared in
a manner similar to Example 2, 210 grams of decyl alcohol,
2U 10 grams of ORTHORIX~ a commercially available calcium
polysulfide product sold by Chevron Chemical Company, San
Francisco, CA, 20 grams of a calcium overbased hydrocarbyl
sulfonate, prepared in a manner similar to Example 5 and
100 grams of Cit-Can 100N oil. The system was heated with
25 agitation to 90°C at which time 148 grams of Ca(OH)2 and
56 grams of sublimed sulfur were charged to the reaction
system. The reaction was then held at 90°C for 45
minutes. Afterwards, the reaction temperature was raised
over a 15 minute period to 150°C whereupon 103 grams of
30 ethylene gly~~ol was added over a 60 minute period. After
complete addition of the ethylene glycol, the reaction
temperature was increased to 160°C and held at this
temperature for 1 hour. At this time, the reaction
temperature eras increased at a rate of 5°C per 20 minutes
J5 until t:he re~~ction temperature reached 175°C whereupon 72
grams of carbon dioxide was charged to the reaction system
over a three hour period. The reaction temperature was
then increased to 195°C and the system stripped under
vacuum (~10 mm of Hg) for a period of 30 minutes.
40 Sediment was removed and 800 ml of 250 thinner which is a
~34~0~2
O1 -28-
mixture of a.romatic:s, paraffins and naphthenes was added
to the system as well as 3 weight percent diatomaceous
05 earth consisting oi= 50~ Hi-Flo, a commercial diatomaceous
earth product available from t9anville, Filtration and
Minerals Division, Denver, CO, and 50~ of 512 Celite, a
commercial c,iatoma<:eous earth product available from
Manville, Filtration and Minerals Division, Denver CO.
The system was filtered through a 1/4 inch Celite pad on a
Buchner funnel. Afterwards, the thinner was removed by
stripping at elevai_ed temperatures and reduced pressures
to yield 500 grams of a calcium overbased sulfurized
alkylphenol having a Total Base Number of 344 (obtained
from second titrimeter); a viscosity of 632 centistokes at
100°C; a sulfur content of 3.31 weight percent; and a
calcium content of :12.8 weight percent.
Example 10
Into a 2--liter, 4 neck flask was added 99 grams
2U of tetrapropenylphcanol, prepared in a manner similar to
Example 3, 7.67 gr.arns of a C20-C28 alkylphenol, prepared in
a manner similar to Example 2, 210 grams of decyl alcohol,
10 grams of 2-mercaptobenzothiazole, 20 grams of calcium
overbased hydrocarbyl sulfonate, prepared in a manner
similar to Example .5 and 100 grams of Cit-Con 100N oil.
The system was hearted with agitation to 90°C at which time
138 grams of calc~ined Dolomite, Ca(Ofi)2.P-Ig(OH)7, and
56 grams of sublimed sulfur were charged to the reaction
system. The reaction was then held at 90°C for 45
minutes. Afterwards, the reaction temperature was raised
over a 15 minute period to 150°C whereupon 103 grams of
ethylene gl~~col waa added over a 60 minute period. After
complete addition of the ethylene glycol, the reaction
temperature was .in~~reased to 160°C and held at this
temperature for L hour. At this time, the reaction
temperature was increased at a rate of 5°C per 20 minutes
until the reaction temperature reached 175°C whereupon
74 grams of carbon dioxide was charged to the reaction
system over a three hour period. The reaction temperature
was then raised to 195°C and the system stripped under
13100
2
O1 -29-
vacuum (~10 mm Hg) for a period of 30 minutes. Sediment
was removed and 800 ml of Chevron 250 thinner, which is a
OS mixture of aromat:ic:s, paraffins and naphthenes was added
to the system as well as 3 weight percent diatomaceous
earth consisting of: 50$ Hi-Flo and 50~ 512 Celite, which
are commercial di.at:omaceous earth products available, from
Manville, Filtration and Minerals Division, Denver, CO.
LO The system was fi.lt:ered through a 1/4 inch Celite pad on a
Buchner funnel. Afterwards, the thinner was removed by
stripping at elevated temperatures and reduced pressures
to yield 280 grams of a calcium-magnesium overbased
sulfurized alkylphe nol having a Total Base Number of 294
15 (obtained from second titrimeter); a viscosity of 154
centistokes at 100°'C; a sulfur content of 3.65 weight
percent; a calcium content of 7.62 weight percent; and a
magnesium content of 2.14 weight percent.
Example 11
2U Into a 1-liter, 3-neck flask was added 104 grams
of tetrapropenylphenol, prepared in a manner similar to
Example 3, 187 grams of a mixture of C18-C30 and C24-C28
alkylphenol, prepared in a manner similar to Example 4,
105 grams of decyl alcohol, 10 grams of 2-mercaptobenzo-
25 thiazole, 20 grams of calcium overbased hydrocarbyl
sulfonate, prepared in a manner similar to Example 5, and
100 grams of Cit-Con 100N oil. The system was heated with
agitation to 90°C at which time 148 grams of Ca(OH)2 and
56 grams of sublimed sulfur were charged to the reaction
30 system. The reaction was then held at 90°C for 45
minutes. Afterwards, the reaction temperature was raised
over a 15 minute period to 150°C whereupon 103 grams of
ethylene glycol wa~~ added over a 60 minute period. After
complete addition of the ethylene glycol, the reaction
3S temperature was increased to 160°C and held at this
temperature for 1 hour. At this time, the reaction
temperature was increased at a rate of 5°C per 20 minutes
until the reaction temperature reached 175°C whereupon
72 grams of carbon dioxide was charged to the reaction
40 system over a three hour period. The reaction temperature
134~~~2
O1 -30-
was then raised to 195°C and the system stripped under
vacuum (~10 mm Hg) for a period of 30 minutes. Sediment
05 was removed and 800 ml of Chevron 250 thinner, which is a
mixture of aromatics, paraffins and naphthenes, was added
to the system as well as 3 weight percent diatomaceous
earth consi=_;ting o1. 50$ of Hi-Flo and 50~ 512 Celite,
which are commercial diatomaceous earth products available
from Manville, Fili_ration and Minerals Division, Denver,
CO. The sy~.tem was filtered through a 1/4 inch Celite pad
on a Buchner funnell. Afterwards, the thinner was removed
by stripping at elevated temperatures and reduced
pressures to yield 601 grams of a calcium overbased
sulfurized alkylphenol having a Total Base Number of 349
(324 TBN on second titrimeter), a viscosity of 441
centistokes at 100"C; a sulfur content of 4.27 weight
percent; and a calcium content of 12.4 weight percent.
Example 12
2U Into a 1-liter, 3 neck flask was added 102 grams
of tetrapropenylphe nol, prepared in a manner similar to
Example 3, 187 grams of a mixture of C18-C30 and C24-C28
alkylphenol, prepared in a manner similar to Example 4,
105 grams of decyl alcohol, 20 grams of 2-mercaptobenzo-
thiazo:Le, 20 grams of a polyisobutenyl succinimide
dispersant composition [prepared by reacting 1 mole of
polyisabutenyl succinic anhydride, where the polyisobu-
tenyl group has a number average molecular weight of about
950, with 0.87 mole of tetraethylenepentaamine; then
diluting to about ~~0~ actives with diluent oil - contains
2.1~ nitrogen] and 100 grams of Cit-Con 100N oil. The
system was heated with agitation to 90°C at which time
148 grams of Ca(OH)2 and 56 grams of sublimed sulfur were
charged to the reaction system. The reaction was then
held at 90°C for 45 minutes. Afterwards, the reaction
temperature was raised over a 15 minute period to 150°C
whereupon 103 grams of ethylene glycol was added over a 60
minute period. After complete addition of the ethylene
glycol, the reaction temperature was increased to 160°C
and held at this temperature far 1 hour. At this time,
134~~~2
O1 -31-
the reaction temperature was increased at a rate of 5°C
per 20 minutes until. the reaction temperature reached
OS 175°C whereupon 72 grams of carbon dioxide was charged to
the reaction system over a three hour period. The
reaction temperature was then raised to 195°C and the
system stripped uncler vacuum (~10 mm Hg) for a period of
30 minutes. Sediment was removed and 800 ml of Chevron
250 thinner which is a mixture of aromatics, paraffins and
naphthenes, was added to the system as well as 3 weight
percent diatomaceous earth consisting of 50$ of Hi-Flo and
50$ Celite, which are commercial diatomaceous earth
products available from Manville, Filtration and Minerals
Division, Denver, CO. The system was filtered through a
1/4 inch Celite pad on a Buchner funnel. Afterwards, the
thinner was removed by stripping at elevated temperatures
and reduced aressures to yield a calcium overbased
sulfurized a.lkylphenol having a Total Base Number of 352
2U (obtained from first titrimeter); a viscosity of 893
centistokes ,st 100°C; a sulfur content of 4.02 weight
percent; and a calcium content of 11.3 weight percent.
Example 13
In a mixer containing a hatch, a vent line, an
overhead system connected to a vacuum line (jet), and a
hotwell line, first vent the mixer overhead into the
hotwell. Close the vapor line valve and then purge the
mixer with a slight nitrogen draft. With heat sources
turned off, add 357 gallons of a tetrapropenylphenol,
prepared similarly to Example 3 above, heated at 180°F,
and add 318 <~allons of Cit-Con .100N oil, heated at 70°F.
Add 630 gallons of a C20-C28 alkylphenol, prepared
similarly to Example 2 above, heated at 150°F; 70 gallons
of a calcium overbased hydrocarbyl sulfonate, prepared
similarly to Example 5 above, heated at 200°F; and 866
gallons of decyl alcohol heated at 70°F.
Shirt agitation and then adjust the mixer's
temperature 1.0 15U°F. After shutting off the nitrogen,
134~~~2
O1 -32-
open the hai:ch and charge 275 lbs of 2-mercaptobenzo-
thiazole to the system and after closing the hatch, heat
OS the system at 200°!F for. 4 hours.
After :in:;uring that the mixer is venting through
the.mixer to hotwe:ll line, cool the system to 175°F.
While agitating the system, add 4,010 lbs of hydrated
lime. Open the vapor line to vent through the condensor,
water receiver, to jets. Close the mixer-to-hotwell line,
and adjust t:o 10 inches of Hg. vacuum. Heat to 260°F.
Add 1,327 lk>s sulfur, heated at 250°F. Heat to 300°F over
a period of 1 hour.. At which time, add 274 gallons of
ethylene glycol over a 60 minute period. The ethylene
LS glycol addition is started very slowly and after complete
addition of the ethylene glycol, heat the system to 335°F
over a period of 1 hour. Charge 1,680 lbs of carbon
dioxide over 2 hours and 48 minutes. Upon carbon dioxide
addition, allow t:he temperature to rise to 350°F.
2U After c;omplete carbon dioxide addition, apply
full vacuum - at least 28 inches of Hg. Heat to 400°F.
Hold at these condiLtions for 30 minutes starting once
395°F is reached. Thereupon cool to 350°F and break
vacuum with nitrogen adjusting to 5 psig to yield a
2S calcium overbased a>ulfurized alkylphenol having a Total
Base Number of 327 having a viscosity of 1375 centistokes
at 100°C and containing 12.38 calcium, 3.70 sulfur and
0.8~ crude sediment:. Filter through diatomaceous earth
and dilute with 5 weight percent 130N oil to yield a
30 calcium overbased sulfurized alkylphenol having a TBN of
312, a viscosity of: 660 centistokes at 100°C and
containing 11.6 calcium, 3.32 sulfur and 0.02$ sediment.
Comparative Example A
(Compared to Examples 8 and 9)
3S Into a 1--liter, 4-neck flask was added 99 grams
of tetrapropenylphe nol, prepared in a manner similar to
Example 3, 167 grams of a C20-C28 alkylphenol, prepared in
a manner similar to Example 2, 210 grams of decyl alcohol,
grams of a cal.ciium overbased hydrocarbyl sulfonate,
40 prepared in a manner similar to Example 5 and 100 grams of
1341002
O1 -33-
Cit-Con 100N oil. The system was heated with agitation to
90°C at which time 148 grams of Ca(OH)2 and 56 grams of
05 sublimed sulfur were charged to the reaction system. The
reaction was then held at 90°C for 45 minutes.
Afterwards, the reaction temperature was raised over,a 15
minute perio~9 to 150°C whereupon 103 grams of ethylene
glycol was a~9ded over a 60 minute period. After complete
additian of the ethylene glycol, the reaction temperature
was increased to 160°C and held at this temperature for 1
hour. At this time, the reaction temperature was
increased at a rate of 5°C per 20 minutes until the
reactian tem~~erature reached 175°C whereupon 72 grams of
carbon dioxide was charged to the reaction system over a
three hour p~ariod. The reaction temperature was then
increased to 195°C and the system stripped under vacuum
(~10 mm of Hg) for a period of 30 minutes. Sediment was
removed and 800 ml of 250 thinner which is a mixture of
aromatics, p,~raffins and naphthenes was added to the
system as well as 3 weight percent diatomaceous earth
consisting o:E 50$ Hi-Fla, a commercial diatomaceous earth
product available from Manville, Filtration and Minerals
Division, Denver, C0, and 50$ of 512 Celite, a commercial
diatomaceous earth product available from Manville,
Filtration a:nd Minerals Division, Denver, CO. The system
was filtered through a 1/4 inch Celite pad on a Buchner
funnel. Aft~arwards, the thinner was removed by stripping
at elevated temperatures and reduced pressures to yield
377 grams of a calcium overbased sulfurized alkylphenol
having a Tot,~l Base Number of 296; a viscosity of 667
centistokes at 100°C; a sulfur content of 3.28 weight
percent (ave:rage of 2 runs); and a calcium content of 11.6
weight percent.
Comparative Example B
(Compared to Example 11)
Into a 1-liter, 3-neck flask was added 102 grams
of tetraprop~~nylphenol, prepared in a manner similar to
Example 3, 187 grams of a mixture of C18-C30 and C24-C28
alkylphenol prepared in a manner similar to Example 4, 105
1341 pp2
O1 -34-
grams of decyl alcohol, 20 grams of calcium overbased
hydrocarbyl sulfonate, prepared in a manner similar to
05 Example 5 and 100 grams of Cit-Con 100N oil. The system
was heated with agitation to 90°C at which time 148 grams
of hydrated lime, C',a(OH)2, and 56 grams of sublimed sulfur
were charged to the reaction system. The reaction was
then held at 90°C for 45 minutes. Afterwards, the
reaction temperature was raised over a 15 minute period to
150°C whereupon 103 grams of ethylene glycol was added
over a 60 minute period. After complete addition of the
ethylene glycol, the reaction temperature was increased to
160°C and held at this temperature for 1 hour. At this
time, the reaction temperature was increased at a rate of
5°C per. 20 minutes until the reaction temperature reached
175°C whereupon 72 grams of carbon dioxide was charged to
the reaction system over a three hour period. The
reaction temperature was then raised to 195°C and the
system stripped under vacuum (~10 mm Hg) for a period of
minutes. Sediment was removed and 800 ml of Chevron
250 thinner, which is a mixture of aromatics, paraffins
and naphthen~=s, was added to the system as well as
3 weight percent diatomaceous earth consisting of 50~
25 Hi-flo and 500 512 Celite, which are commercial
diatomaceous earth products available from Manville,
Filtration and Minerals Division, Denver, CO. The system
was filtered through a 1/4 inch Celite pad on a Buchner
funnel. Afterwards, the thinner was removed by stripping
30 at elevated temperatures and reduced pressures to yield
525 grams of a calcium overbased sulfurized alkylphenol
having a Total Base Number of 329 (327 on a second
titrimeter), a viscosity of 1190 centistokes at 100°C; a
sulfur content of 3.75 weight percent; a calcium content
3S of 12.2 weight percent and a crude sediment of 5.2 weight
percent..
Comparative Example C
(Compared to Example 12)
Into a 1-liter, 3 neck flask was added 102 grams
of tetr-apropenylphenol, prepared in a manner similar to
134~D~z
O1 -35-
Example 3, L87 grams of a mixture of C18-C30 and C24-C28
alkylphenol,, prepared in a manner similar to Example 4,
05 105 grams o1: decyl alcohol, 20 grams of a polyisobutenyl
succinimide disper;sant composition [prepared by reacting
1 mole of polyisobutenyl succinic anhydride, where the
polyisobutenyl group has a number average molecular~weight
of about 950, with 0.87 mole of tetraethylene pentaamine;
then diluting to a bout 50$ actives in diluent oil -
contains 2.1.~ nitrogen] and 100 grams of Cit-Con 100N
oil. The s~~stem was heated with agitation to 90°C at
which time 7.48 grams of hydrated lime, Ca(OH)2, and
56 grams of sublimed sulfur were charged to the reaction
l5 system. The reac:t:ion was then held at 90°C for 45
minutes. Afterwards, the reaction temperature was raised
over a 15 minute period to 150°C whereupon 103 grams of
ethylene glycol wa:> added over a 60 minute period. After
complete addition of the ethylene glycol, the reaction
temperature was increased to 160°C and held at this
temperature for 1 hour. At this time, the reaction
temperature was increased at a rate of S°C per 20 minutes
until the reaction temperature reached 175°C whereupon
72 grams of carbon dioxide was charged to the reaction
system over a three hour period. The reaction temperature
was then raised to 195°C and the system stripped under
vacuum (~10 mm Hg) for a period of 30 minutes. Sediment
was removed and 800 ml of Chevron 250 thinner, which is a
mixture of aromat.ic:s, paraffins and naphthenes, was added
to the system as well as 3 weight percent diatomaceous
earth consisting of: 50$ Hi-Flo and 50~ 512 Celite, which
are commercial diatomaceous earth products available from
Manville, Filtration and Minerals Division, Denver, CO.
The system was filtered through a 1/4 inch Celite pad on a
3S Buchner funnel. Afterwards, the thinner was removed by
stripping at elevated temperatures and reduced pressures
to yield a calcium overbased sulfurized alkylphenol having
a Total Base Number of 331 (on first titrimeter), a
viscosity of 907 centistokes at 100°C; a sulfur content of
1341 00 2
O1 -36-
3.94 weight percent.; and a calcium content of 10.3 weight
percent.
05 Comparative Example D
(Compared to Example 6)
Into a 2-liter, 4-neck flask was charged
104 grams of tetrapropenylphenol, prepared in a manner
similar to Example 3, 178 grams of C18-C30 alkylphenol,
prepared in a manner similar to Example 1, 105 grams of
decyl alcohol, 20 grams of a calcium overbased hydrocarbyl
sulfonate, prepared in a manner similar to Example 5 and
100 grams of Cit-Con 100N oil. The system was heated with
agitation at 90°C at which time 148 grams of Ca(OH)2 and
56 grams of sublimed sulfur were charged to the reaction
system. The reaction system was then held at 90°C for 45
minutes. Afterwards, the reaction temperature was raised
over a 15 minute period to 150°C whereupon 103 grams of
ethylene glycol was added over a 60 minute period via an
2U addition fun!1e1. After complete addition of ethylene
glycol, the reaction temperature was increased to 160°C
over a 15 minute period and held at this temperature for 1
hour. At this time, the stirring rate of the reaction
mixture was increased to moderately fast, and the reaction
temperature was then increased at a rate of 5°C per 20
minutes until the reaction temperature reached 175°C
whereupon 72 grams of carbon dioxide was charged through a
flowmeter to the reaction system over a three hour
period. The reaction temperature was then increased to
195°C and the system stripped under vacuum (~10 mm Hg) for
a period of 30 minutes to yield 608 grams of product which
was purified by addition of 3 weight percent of
diatomaceous earth consisting of 50~ Hi-Flo and 50~ Celite
512, commercial diatomaceous earth products available from
Manvil7.e, Filtration and Minerals Division, Denver, CO,
followed by Filtration through a 1/4 inch Celite paid on a
Buchner funnel. The resulting product has a total base
number of 33'5 (335 TBN on second titrimeter); a viscosity
of 1323 centistokes at 100°C; a sulfur content of 3.95;
and a calcium content of 12.5x.
1341002
O1 -37-
Table T below illustrates the side-by-side
comparison of some of the Examples with the Comparative
05 Examples.
TABLE
I
Viscosity4~ight~ Wbight Crude
$
Catalyst TBN (100C) SulfurCalcium Sediment
Example 8 MBT 3283365 3.96 12.3 1.20
Centistokes
Example 9 o:RTHORIX~3448632 3.31 12.8 4~
Centistokes
LS Canparative I~~ne 2968667 3.28 11.6 7.2~
Example A Centistokes
Example 11 MBT 349A441 4.27 12.4 2.8~
Centistokes
Comparative None 329A1190 3.75 12.2 5.2~
Example B Centistokes
Example 12 P93T 352A893 4.02 11.3 2.8~
Centistokes
Canparative None 331A907 3.94 10.3 3.2~
25 Example C Centistokes
Example 6 Mi3T 3408720 4.4 12.3 1.4~
Centistokes
Comparative None 33681323 3.95 12.5 2.4~
Example D Centistokes
30
A - TBN value 1_ranfirsttitrimeter
the
B - TBN value ~'romsecondtitrimeter
the
Table :I demonstrates t, under milarconditions,
tha si use
of a sulfurizationcatalyst generally ults in higher
res a
3S
TBN product of r cosity, with lower
lowe vis and crude
sediment than is ailable withoutuse a sulfurization
av of
catalyst.
1341pp2
-38-
01
In Table~~ II and III below, Examples 14-17
further illustrate high TBN, low viscosity products of
05 this invention. These products were prepared similarly to
Examples 6-.13 above.
15
2U
30
40
1341 pd~,
N
I I C d O
O .~ o ~
w E~ E ro .., w
a~ ~
C \ .~d' d' ~' '., C U ~ N
ro
N r-I O N N N ~ \O pp
S.1 O IJ .-r
y.., ~o t~ U ~ N I~
N N N N N ro .-~,-1 ~ 1J ro
~ ?~ U .C U ro .-i
.~
~ r-1 O I i U N 3 .~
O
a~ cn ~ .~ .~ ro
~
O ~
.- 3 C ~ rt
i
O O ro O. ..
w ~-I
O W
>., 0 0 0 ~ N r r U 3 ~
,~
N U ~-~~ .~ O VI M M C W
O
U N N N ri ro ro ~ rl
ro p .O o o x vy m
r-,
s~ ro
a, ~ 'v 'v ro
C C 3 ~ u1 ~ S.i
O ro ro ~ C~ N O
O O ro 'O +~
z c~ .
~
w .u o o ~ a~ e~ .n
ro ,-~.-~~ ,~ .~ c c o 'v ,-~ ,~
\ ~ N N N N U ~ U
N r-I ~ .C O w ro C
O U N N 'N N ro ~'-Ga U r-I r-1 ri
-1
V wn U ry r-I ro C .-i
O ~ ~ +~ U m ro
ro C C .-I-a ~r ~
a~ a~ w E ~ ro O
w CL ~ w N O w
O O O ~ ~ C1 >.
y..~ fN IN ~ U ri ro
o N ro ro ~ ~ ro
~ c
'v
H U7 ri O O O O ro ~ S.~ C O .~ .-i G
'-, ,-,~, .-~ ~, ~ .u ro s~ U v ro
~ a~
t ~ a, a~ a~ ~ > --~ s..
r-,
s~ ro +~ .~ o a~ ro a~ ~
U
N N N H U
ro ~
..i+~ O
F' O O O .~ w .c U ro
N C w ~ ~ Cx O t7~ -..r
~
" ~ .,~ o .,~ ro .~
o
N x >, t~ l~ w C ~ p,
N
H O z ~'~~''~ O O 3 I ri
C
x x ~ o a~
ro ~C O Q, 0 o C y >., m .p
0 ,t~
w x ~ ,~ ,. ,. o ro .c: d'
~ ro
ro Eic>~E-~H N ~ ~ I
O
U W O G..'C7 C r-1r-I ~ C da >C .a
~
C ~
N V C r~ N G P.~
~
1 N N C O O
~
' O U ~ ~ ~ ~ w UI .N .
b
t1, C ~ f.1i1 f.~C ~ U7
-~ ~
'O .--W1 O r~ ~ ~r ro
U ?i
\ ro I W tD ~D C ~ ?~ w ro ro H ro
C C
L.i O M M M o w ,x x ,~ ..~ +.~ x
LI
C U O ~ .-I r-IU C w
~ ~-I
w U N N N N ro ~ ro ro f'I O O 'O
rl O
r-~ r-a r-1 ~ N U C
.~ U7 O .C
C O .-i r-IO .-i U ~ JJ ro
g C C1
tn ~ ro ro C ro la ~ .C .~
ro N Li
O
N O~ O .C ~ U ~ -
O ~
C1
o ~ ~~~ od 33
' ro
x
0.~ 3 ~ w >r U
+~ w ~-
x
ro t~c~ r. r .-a ~ ,x 1 I ~y
O O
.~
r O ~ ro roN
~
N N N N ~b ~ ro
U
,..H+ II
~
v' .C oo H
ro O O
O
~
~ o r, ' ~ ~ o
~ ~
ro
~
x
w N N x o ~ ~ C-
~ oo ~
na ro U o ~ O e1
o o U
* ro II II
.-I II
x ~
x c'u1 ~ 1~ W fn f1 .
W r-1.-Iri H * FC f~ r1 N
~
.-1 If1 O ~ O
O O ~~ ~ N N
1341pp2
O1 -40-
TABLE III
05 Viscosity Weight Weight Crude
~ $
TBN (100C Sulfur Calcium Sediment
Ex. .l4C 338 561128 4.3 12.2 2.8
Ex. 15 324 360 3.74 12.4 2.6
Ex. 16 337 501 3.49 12.7 2.0
Ex. 17 331 424 4.1 12.7 1.6
C - after a 3~ dilution with Cit-Con 100N.
The Group II metal overbased sulfurized
alkylphenols of this invention are characterized by
containing at least about 90~ and preferably at least 95$
of Group II metal s~ulfurized alkylphenols in the actives
and no more than about 10~ and preferably no more than
about 5~ of Group I:I metal unsulfurized alkylphenols in
the actives. Prior art Group II metal overbased
2U sulfurized alkylphe~nols of 300+ TBN contain significantly
more than 10~ of Group II metal unsulfurized alkylphenol
in the actives. Prior art compositions can be prepared
either by a one step process as in Comparative
Examples A-C above or in a two step process as shown in
Comparative Example E below.
Comparative Example E
STEP 1 - Formation. of Sulfurized Alkylphenol Calcium Salt
Into a 3--liter, 3-neck flask was added 529 grams
of tetrapropenylphe>nol, prepared in a manner similar to
Example 3. 274 grams of a C18-C30 alkylphenol, prepared
in a manner similar to Example 1, 250 grams of Cit-Con
100N. The ~~ystem was heated to 90°C and 50 grams of
Ca(OH)2 and 112.5 drams of sublimed sulfur were added.
The system eras heated to 175°C and 32.5 grams of ethylene
glycol was added over thirty minutes. The system was held
at 175°C for one hour and then vacuum (~10 mm Hg) was
applied for four hours to strip the ethylene glycol.
127.5 grams of C15-C18 alpha olefin derived frorn cracked
wax was added at 1:35°C along with 122.5 grams of Cit-Con
100N and the system heated for 8 hours under nitrogen.
1341 p02
O1 -41-
The product was :Filtered through a 50-50 mixture of Hi-Flo
and Celite !>12, diatomaceous earth products available from
OS Manville, Filtration and Minerals Division, Denver, CO, to
give 1351 grams of product with a Total Base Number of 63
containing _1.94 weight percent of calcium and 4.47 weight
percent of sulfur.
STEP 2 - Formation of Overbased Sulfurized Alkylphenol
Calcium Salt
Into a 1~-.liter, 3-neck flask was added 380 grams
of the product prepared in Step 1, 20 grams of a polyiso-
butenyl succ:inim:ide dispersant composition [prepared by
reacting 1 rnole of polyisobutenyl succinic anhydride,
where the polyisobutenyl group has a number average
molecular weight of 950, with 0.87 mole of tetraethylene
pentaamine, then diluting to about 50$ actives with
diluent oil], 48 grams of decyl alcohol and the system was
heated to 90°C; 106 grams of Ca(OH)2 was added while the
2U system was heatec9 to 150°C. Ethylene glycol, 74.5 grams,
was slowly <~dded and the system heated to 175°C. Carbon
dioxide, 61 grams, was added over a period of 4 hours.
The product was .stripped under vacuum (~10 mm Hg) at
190°C, filtered through a 50-50 mixture of Hi-Flo and
Celite 512, diatomaceous earth products available from
Manville, Filtration and Minerals Division, Denver, CO, to
' yield 485 grams of a calcium overbased sulfurized alkyl-
phenol having a 'Cotal Base Number of 334, a viscosity of
2405 centist:okes at 100°C; a sulfur content of 2.7 weight
percent; anct a calcium content of 12.1 weight percent.
The compositions of this invention as well as
prior art compositions were analyzed by the following
dialysis anti 1H-cdMR technique (Example 18) to determine
the content of Group II metal sulfurized alkylphenol as
well as unsulfurized Group II metal alkylphenol.
1341002
O 1 -4 2-
Example la
The compositions of this invention as well as
05 prior art compositions are analyzed in the following
manner. The Group II metal overbased sulfurized alkyl-
phenol additive (5CI grams) is weighed into an acetone-
rinsed dialysis bag (Ramses No. 18 prophylactic bag).. The
bag is suspended in a 2-liter beaker containing 1.5 liters
LO of 60 volume percent of methyl ethyl ketone (MEK), and 40
volume percent t-butanol. The solution is stirred with a
magnetic stirrer at: ambient temperature. The solution is
changed every 24 hours for seven days. The combined
dialyzate solutions are stripped using a rotary evaporator
15 and finally at 1 mm Hg vacuum at 85°C to yield a product
which is weighed. This product contains diluent oil
(Cit-Con 100N) and unsulfurized alkylphenol starting
material as determined by 1H-C7P1R in hexamethyl-
phospho ramide (f~MPA) solvent. In this solvent the
ZO unsulfurized alkylp henol shows peaks in the 1H-NMR at
10.00 to 10.11 ppm relative to tetramethylsilane (TMS)
added as an internal standard. The alkylphenols of
Examples 1-4 show this 1H-NM R peak and so it is diagnostic
for unsulfurized al.kylphenol.
25 The solid residue in the dialysis bag is
weighed. This residue contains greater than 95 percent of
all the calcium (or- other Group II metal) in the original
Group :II metal overbased sulfurized alkylphenol prepara-
tions and is referred to as the "actives". This residue
30 or "actives" cont.ai.ns the calcium sulfurized overbased
alkylphenol and any unsulfurized calcium alkylphenol. The
composition of the "actives" is determined by the follow-
ing analysis. The "actives" are dissolved in mixed
hexanes and then treated with 100 ml of concentrated
35 hydrochloric acid inn 100 ethanol. After the hydrochloric
acid addition the mixture is stirred for one hour at
ambient temperature to effect complete decalcification of
the "actives". 7.'he liberated sulfurized alkylphenol and
in some cases the unsulfurized alkylphenol are obtained by
40 water washing the hexane solution; washing the hexane
1341 002
O1 -43-
solution with 10 p<~rcent aqueous sodium bicarbonate; and
then stripping the hexane solution at 120 mm Hg at 80-85°C
05 to yield the: decalcified "actives" product which are
analyzed by 1H-NP1R in hexamethylphosphoramide (HP1PA) as
solvent containing TR1S as internal standard. The
unsulfurized alkylp henol shows a peak at 10.00 to 10.11
and is referred to as the SO peak. The sulfurized
LO alkylphenol=_. show peaks at 10. Q0-10.50 for the monosulfide
bridged alk~~lpheno:Ls and is referred to as the S1 peak.
The sulfuri::ed alkylphenols also show peaks at 10.90 to
11.00 for the disu:Lfide bridged alkylphenols and is
referred to as the S2 peak. The areas for these peaks are
15 obtained by integration on a Varian T60'~or a General
Electric QE--300~t1H:a NMR spectrometer. The integrated
areas are converte<9 to mole percents by dividing the S1
and S2 integrated peak area by two (assuming dimeric
structures).
20 A=_. used Inerein and described above, the term
"actives" is a measure of the amount of the Group II metal
unsulfurized alkylphenol and the Group II metal sulfurized
alkylphenol contained in the composition which can be
determined by this procedure as well as other standard
25 analytical techniques.
30 ~ T~-ao~- l'~arl~
40
1341002
01
-44-
TABLE IV
OS ANAL~'SIS OF ACTIVES OBTAINED FROP4 EXAP9PLE 18
dole of
Percent
actives Viscosity
as
SO() Sl(2) S2(3) TBN (cSt-100C)
Example 11 0 30 70 349 441
Comparative 15 20 65 333 538
Example B
Example 12 U 34 66 352 893
Comparative 18 29 53 331 907
Example C
Comparative 16 25 59 334 2,405
Example E
2U 1. SO = mole percent of calcium (unsulfurized alkylphenol)
2. Sl = mole percent of calcium (monosulfide alkylphenol)
3. S2 = mole percf>nt of calcium (disulfide alkylphenol)
Table V below establishes that Group II metal
unsulfurized alkylphenol content is detrimental to a
Group II metal overbased sulfurized alkylphenol composi-
' tion. In particular, as shown in this table, the calcium
salt of the alkylphenol of Example 3 is extremely viscous
and accordingly, i1E present in significant amounts, it
will significantly increase the viscosity of the Group II
metal overbased su_Lfuri.zed alkylphenol composition.
Likewise, the calcium salt of the alkylphenol of Example
4, while being much less viscous than the calcium salt of
the alkylphe~nol of Example 3, does not contribute much to
the Total Base Number of the composition. Accordingly, if
present in ~,ignificant amounts, it will significantly
decrease the Total Base Number of the Group II metal
overbased sulfur:LZed alkylphenol composition. On the
other hand, the Group II metal overbased sulfurized
alkylphenols of 1=his invention contain little if any of
the unsulfurized Group II metal alkylphenols and
1341002
O1 -45-
accordingly possess a high Total Base Number and an
acceptable viscosity. The results of Example 6 are
OS included for illustrative purposes.
' TABLE V
TBN Viscosity (100°C)
calcium salt of the (a) too viscous to
alkylphenol of Ex. 3 211 measure
50$ dilution with
Cit-Con 100N 105 112 centistokes
calcium salt of the (a)
alkylphenol of Ex. 4 54 18 centistokes
(represents approx.
50$ conveys ion)
Example 11 349 441 centistokes
(a) prepared by reacting the alkylphenol with excess
hydrated lime (0.66 eq.) in ethylene glycol at 175°C
Example 19
A formulated oil containing a Group II metal
overbased sulfurized alkylphenol of the invention was
tested in a Sequence V-D Test method (according to
candidate test for ASTt9). This procedure utilizes a Ford
' 2.3-liter, four-cylinder Pinto engine. The test method
simulates a type of severe field test service
characterized by a combination of low speed, low
temperature "stop a.nd go" city driving and moderate
turnpike operation. The effectiveness of the additives in
the oil is measured, in terms of the protection against
sludge and varnish deposits on a 0 to 10 scale with 0
being black~and 10 indicating no varnish or sludge
deposits. The results are indicated in Table VI.
Sequence V-D test was run using a product
prepared similarly to that described in Examples 6 and
7. These products were compared to a 250 TBN commercial
calcium sulfurized alkylphenol prepared from alkylphenol
described in Example 3.
~rU~.e .. /~~CL Y
~34~~~2
O1 -46-
The compositions of the formulated oils were:
5.25$ of a bis-polyisobutenyl succinimide; 20 millimoles
OS per kilogram of an overbased hydrocarbyl sulfonate as
described in Example 5; 20 millimoles per kilogram of a
320 TBN hydrocarby.l sulfonate, 82 millimoles per kilogram
of the product prepared similarly to Examples 6 and "7, 20
millimoles per kilogram of a zinc dithiophosphate; 20~ of
~0 a commercial. viscosity index improver in 150N/600N Exxon
base oil - f15~ by weight 150Pd and 15~ by weight 600N.
The comparative reference formulation used the
same formulation as above with the exception that 82
millimoles per kilogram of a commercial 250 TBN phenate
15 prepared from the alkylphenol described in Example 3 was
used instead of the high TBN phenate prepared similarly to
Examples 6 and 7.
SEQUENCE V-D RESULTS
2U gormulation Deposit
containing the
Phenate of AS(1) AV(2) PV(3)
Prior Art (run in 1983) 8.34 7,g4 x.94
(run in 1984) 8.9 8.0 8.0
(run in 1985) 8.9 7,7 8.0
High TBN Phenate
prepared
similarly to
Examples 6 and 7(5) 9.6 9.0 8.8
(Run in 1985)
(1) average sludge
(2) average varni=.h
(3) piston varnish.
( 4) average of 6 runs
(5) average of 2 runs
~ 1~ra~..~-j'l;c~,~
