U.S. patent application number 08/696885 was filed with the patent office on 2002-07-11 for overbased alkyl oxy benzene sulfonates as detergents.
Invention is credited to KING, WILLIAM F., LOCKETT, STEVEN G., NELSON, RICHARD J..
Application Number | 20020091069 08/696885 |
Document ID | / |
Family ID | 24798934 |
Filed Date | 2002-07-11 |
United States Patent
Application |
20020091069 |
Kind Code |
A1 |
KING, WILLIAM F. ; et
al. |
July 11, 2002 |
OVERBASED ALKYL OXY BENZENE SULFONATES AS DETERGENTS
Abstract
A marine lubricating oil has a major amount of oil of
lubricating viscosity; and a minor amount of an overbased, alkyl
oxy benzene sulfonate having a TBN of at least 200. Between 40 wt.
% and 80 wt. % of the alkyl group is attached at the 4-position and
higher positions of the alkyl group. The oxy group can be hydroxy,
methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy.
Inventors: |
KING, WILLIAM F.; (NOVATO,
CA) ; NELSON, RICHARD J.; (PINOLE, CA) ;
LOCKETT, STEVEN G.; (SAN RAFAEL, CA) |
Correspondence
Address: |
CHEVRON CORPORATION LAW DEPARTMENT
PATENT DIVISION
PO BOX 6006
SAN RAMON
CA
94583-0806
US
|
Family ID: |
24798934 |
Appl. No.: |
08/696885 |
Filed: |
November 26, 1996 |
PCT Filed: |
December 7, 1995 |
PCT NO: |
PCT/US95/16162 |
Current U.S.
Class: |
508/398 ;
508/401; 508/402 |
Current CPC
Class: |
C10M 2215/08 20130101;
C10M 2219/066 20130101; C10N 2040/044 20200501; C10M 2211/044
20130101; C10M 2219/088 20130101; C10N 2040/28 20130101; C10M
129/76 20130101; C10M 2215/30 20130101; C10M 2223/042 20130101;
C10M 2219/087 20130101; C10M 2223/04 20130101; C10M 2227/062
20130101; C10M 129/40 20130101; C10M 2215/042 20130101; C10M
2219/089 20130101; C10M 2223/045 20130101; C10M 2207/023 20130101;
C10M 2215/226 20130101; C10M 2227/00 20130101; C10M 2227/061
20130101; C10M 131/06 20130101; C10M 137/10 20130101; C10M 159/24
20130101; C10M 2207/287 20130101; C10M 2207/288 20130101; C10N
2040/042 20200501; C10M 2227/06 20130101; C10M 2207/126 20130101;
C10M 2215/066 20130101; C10M 2215/082 20130101; C10N 2040/253
20200501; C10N 2040/251 20200501; C10N 2040/252 20200501; C10M
129/95 20130101; C10M 131/12 20130101; C10N 2040/08 20130101; C10M
2207/262 20130101; C10M 2207/026 20130101; C10M 2227/066 20130101;
C10M 2215/22 20130101; C10N 2040/04 20130101; C10M 135/18 20130101;
C10M 135/20 20130101; C10M 139/00 20130101; C10M 2215/225 20130101;
C10M 2215/064 20130101; C10M 133/12 20130101; C10M 2207/125
20130101; C10M 2215/068 20130101; C10M 129/10 20130101; C10M
2209/104 20130101; C10M 2219/022 20130101; C10N 2040/255 20200501;
C10M 2215/067 20130101; C10M 2227/063 20130101; C10N 2010/04
20130101; C10N 2010/12 20130101; C10M 2205/026 20130101; C10M
2215/06 20130101; C10M 2227/065 20130101; C10M 2229/051 20130101;
C10M 2207/024 20130101; C10M 2207/289 20130101; C10M 2215/28
20130101; C10M 133/08 20130101; C10M 2219/044 20130101; C10M
2219/046 20130101; C10M 2215/221 20130101; C10M 163/00 20130101;
C10M 133/56 20130101; C10M 2207/027 20130101; C10M 2207/34
20130101; C10M 2205/00 20130101; C10M 2209/084 20130101; C10M
2211/06 20130101; C10M 2215/086 20130101; C10N 2040/046 20200501;
C10M 2207/129 20130101; C10M 2211/022 20130101; C10M 2219/08
20130101; C10N 2040/25 20130101; C10M 129/14 20130101; C10M
2215/065 20130101; C10M 2219/068 20130101; C10M 135/02 20130101;
C10M 2219/02 20130101; C10M 2219/024 20130101; C10M 2205/06
20130101; C10M 2211/024 20130101 |
Class at
Publication: |
508/398 ;
508/401; 508/402 |
International
Class: |
C10M 159/24 |
Claims
What is claimed is:
1. An additive comprising an overbased, alkyl oxy benzene sulfonate
having a TBN of at least 200, wherein between 40 wt. % and 80 wt. %
of the alkyl group is attached at the 4-position and higher
positions of the alkyl group, and wherein the oxy is selected from
the group consisting of hydroxy, methoxy, ethoxy, propoxy, butoxy,
pentoxy, and hexoxy.
2. An additive according to claim 1 wherein the overbased, alkyl
oxy benzene sulfonate is produced by a process comprising: (a)
alkylating an oxy benzene with an olefin having between 40 wt. %
and 80 wt. % internal olefins to produce an alkyl oxy benzene; (b)
sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene
sulfonic acid; and (c) overbasing the alkyl oxy benzene sulfonic
acid to produce the said overbased, alkyl oxy benzene
sulfonate.
3. An additive produced by a process comprising: (a) isomerizing an
olefin using an iron pentacarbonyl catalyst to produce an
isomerized olefin; (b) alkylating an oxy benzene with the
isomerized olefin to produce an alkyl oxy benzene, wherein the oxy
is selected from the group consisting of hydroxy, methoxy, ethoxy,
propoxy, butoxy, pentoxy, and hexoxy; (c) sulfonating the alkyl oxy
benzene to produce an alkyl oxy benzene sulfonic acid; and (d)
overbasing the alkyl oxy benzene sulfonic acid to produce an
overbased, alkyl oxy benzene sulfonate having a TBN of at least
200.
4. An additive produced by a process comprising: (a) alkylating an
oxy benzene, wherein the oxy is selected from the group consisting
of hydroxy, methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy,
with a polyalpha olefin having an activity of at least 80% to
produce an alkyl oxy benzene; (b) sulfonating the alkyl oxy benzene
to produce an alkyl oxy benzene sulfonic acid; and (c) overbasing
the alkyl oxy benzene sulfonic acid to produce an overbased, alkyl
oxy benzene sulfonate having a TBN of at least 200.
5. An additive according to claim 1, 3, or 4 wherein the overbased,
alkyl oxy benzene sulfonate has a TBN of at least 250.
6. An additive according to claim 1 or 3 wherein between 45 wt. %
and 70 wt. % of the alkyl group is attached at the 4-position and
higher positions of the alkyl group.
7. An additive according to claim 1, 3, or 4 wherein the oxy group
is hydroxy.
8. An additive according to claim 1, 3, or 4 wherein the alkyl
group has from eighteen to thirty carbon atoms per alkyl group.
9. An additive according to claim 8 wherein the alkyl group has
from twenty to twenty-four carbon atoms per alkyl group.
10. A lubricating oil comprising: (a) a major amount of base oil of
lubricating viscosity; and (b) a minor amount of the additive
according to claim 1, 3, or 4.
11. A lubricating oil according to claim 10 wherein the lubricating
oil is a marine lubricating oil.
12. A lubricating oil according to claim 10 further comprising an
ashless dispersant and a zinc dialkyldithiophosphate.
13. A lubricating oil according to claim 10 further comprising a
viscosity index improver.
14. A lubricating oil according to claim 10 further comprising a
detergent selected from the group consisting of metal phenates,
metal sulfonates, and metal salicylates.
Description
[0001] The present invention relates to an additive especially
useful in a marine lubricating oil.
BACKGROUND OF THE INVENTION
[0002] U.S. Pat. No. 3,523,898 teaches that overbased alkyl phenol
sulfonic acids are useful as detergents in lubricating oils. The
alkyl groups appear to be attached at either the 1- or 2-position
of the alkyl groups, and the TBN appears to limited to 150 or
less.
[0003] British 1,372,532 teaches that mixtures of overbased, alkyl
hydroxy benzene sulfonates and alkylsalicylic acids are useful in
lubricating oils. The alkyl groups of the sulfonates appear to be
attached at either the 1- or 2-position of the alkyl groups. The
TBN appears to be about 200.
[0004] British 1,332,473 teaches that overbased, alkyl hydroxy
benzene sulfonates are useful as an oil-soluble dispersant in
lubricating oils. The patent is silent as to where the alkyl groups
are attached. The TBN appears to be about 400, with a very high
base ratio.
[0005] U.S. Pat. No. 4,751,010 teaches that partial sulfonation of
alkylphenol results in the formation of an alkyl hydroxy benzene
sulfonate that can be overbased using sulfurization and
carbonation. The patent is silent as to where the alkyl groups are
attached. The TBN appears to be in the range of from 200 to
250.
[0006] U.S. Pat. Nos. 5,330,663 and 5,330,664 teach overbased
alkylphenoxy sulfonates that have alkyl groups derived from
substantially straight-chained olefins that are either internal or
alpha. It does not teach using olefins that are partially internal
olefins.
[0007] U.S. Pat. Nos. 3,523,898; 4,751,010; 5,330,663; and
5,330,664 are all hereby incorporated by reference for all
purposes.
SUMMARY OF THE INVENTION
[0008] The present invention provides a lubricating oil having a
major amount of base oil of lubricating viscosity; and a minor
amount of an overbased, alkyl oxy benzene sulfonate having a TBN of
at least 200, preferably at least 250, between 40 wt. % and 80 wt.
% of the alkyl group is attached at the 4-position and higher
positions of the alkyl group. Preferably, between 45 wt. % and 70
wt. % of the alkyl group is attached at the 4-position and higher
positions of the alkyl group. This lubricating oil is especially
useful as a marine lubricating oil.
[0009] The oxy group can be either hydroxy, methoxy, ethoxy,
propoxy, butoxy, pentoxy, or hexoxy. Preferably, it is hydroxy.
[0010] Preferably, the alkyl group of the overbased, alkyl oxy
benzene sulfonate has from eighteen to thirty carbon atoms per
alkyl group. More preferably, it has from twenty to twenty-four
carbon atoms per alkyl group.
[0011] One process for making this overbased, alkyl oxy benzene
sulfonate comprises alkylating an oxy benzene with an olefin
between 40 wt. % and 80 wt. % internal olefins to produce an alkyl
oxy benzene, then sulfonating the alkyl oxy benzene to produce an
alkyl oxy benzene sulfonic acid; and overbasing the alkyl oxy
benzene sulfonic acid to produce the overbased, alkyl oxy benzene
sulfonate. Preferably, the internal olefin is produced by
isomerizing an olefin using an iron pentacarbonyl catalyst.
[0012] In an alternative embodiment of the present invention, an
additive is produced by alkylating an oxy benzene with a polyalpha
olefin having an activity of at least 80% to produce an alkyl oxy
benzene, sulfonating the alkyl oxy benzene to produce an alkyl oxy
benzene sulfonic acid, and overbasing the alkyl oxy benzene
sulfonic acid to produce an overbased, alkyl oxy benzene sulfonate
having a TBN of at least 200, preferably at least 250.
DETAILED DESCRIPTION OF THE INVENTION
[0013] In its broadest aspect, the present invention involves
highly overbased, alkyl oxy benzene sulfonate detergents where at
least 40 wt. % of the alkyl groups are attached at the 4-position
and higher positions of the alkyl group. When at least 40 wt. % of
the alkyl groups are attached at the 4-position and higher
position, the viscosity is lowered significantly.
[0014] On the other hand, at least 20 wt. % of the alkyl groups
should be attached at the 1-, 2-, and 3-position in order to reduce
high temperature deposit formation. While Applicants do not wish to
be bound by any particular theory of operation, it is believed that
too high of internal attachment leads to structures that are
similar to materials derived from branched olefins. Such materials
tend to decompose readily at the branching.
[0015] In one embodiment, between 40 wt. % and 80 wt. % (preferably
between 45 wt. % and 70 wt. %) of the alkyl group is attached at
the 4-position and higher positions of the alkyl group. This type
of additive can be produced by alkylating an oxy benzene with an
olefin containing between between 40 wt. % and 80 wt. % internal
olefins to produce an alkyl oxy benzene, sulfonating the alkyl oxy
benzene to produce an alkyl oxy benzene sulfonic acid; and
overbasing the alkyl oxy benzene sulfonic acid to produce the
overbased, alkyl oxy benzene sulfonate. An olefin containing
between 20 wt. % and 60 wt. % internal olefins can be formed by
isomerizing an alpha olefin using an iron pentacarbonyl
catalyst.
[0016] In another embodiment, the additive is produced by
alkylating an oxy benzene with a polyalpha olefin having an
activity of at least 80% to produce an alkyl oxy benzene,
sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene
sulfonic acid; and overbasing the alkyl oxy benzene sulfonic acid
to produce an overbased, alkyl oxy benzene sulfonate having a TBN
of at least 250.
[0017] The present invention comes out of work in trying to find an
inexpensive alternative to the use of salicylates in lube oils for
marine applications. That alternative should have a TBN of over
250, have a viscosity of less than 600 cSt, and have comparative
properties with commercial salicylates.
[0018] The initial attempts were with an overbased oxy benzene
sulfonate having a linear C.sub.20-C.sub.28 alkyl group. That
material turned out to be so viscous that its viscosity could not
be measured. It was so viscous that it didn't flow from a beaker
even when left overturned for over a weekend.
[0019] We overcame this problem by using an overbased alkyl oxy
benzene sulfonate having alkyl groups that were isomerized prior to
alkylation of the benzene. It is essential that alkyl groups of the
overbased alkyl oxy benzene sulfonate be predominately attached at
the 4-position and higher positions of the alkyl group.
THE OVERBASED ALKYL OXY BENZENE SULFONATE
[0020] The lubricating oil has a minor amount of an overbased,
alkyl oxy benzene sulfonate having a TBN of at least 200,
preferably at least 250, wherein at least 40 wt. % of the alkyl
group of the sulfonate is attached at the 4-position and higher
positions of the alkyl group. The oxy group can be either hydroxy,
methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy. Preferably,
it is hydroxy.
[0021] By "TBN," we mean "Total Base Number," which refers to the
amount of base equivalent to one milligram of KOH in one gram of
additive. Thus, higher TBN numbers reflect more alkaline products
and therefore a greater alkalinity reserve. The Total Base Number
for an additive composition is readily determined by ASTM test
method D664 or other equivalent methods.
[0022] By "internal olefins," we mean an olefin wherein the double
bond is at the 4-position and higher positions of the alkene,
instead of at the 1-, 2-, or 3-position.
[0023] Preferably, the alkyl group of the overbased, alkyl oxy
benzene sulfonate has from eighteen to thirty carbon atoms per
alkyl group. More preferably, the alkyl group has from twenty to
twenty-four carbon atoms per alkyl group.
[0024] The additive of the present invention can be produced by
alkylating an oxy benzene with an olefin containing between 40 wt.
% and 80 wt. % internal olefins to produce an alkyl oxy benzene,
sulfonating the alkyl oxy benzene to produce an alkyl oxy benzene
sulfonic acid; and overbasing the alkyl oxy benzene sulfonic acid
to produce the overbased, alkyl oxy benzene sulfonate. An olefin
containing between 40 wt. % and 80 wt. % internal olefins can be
formed by isomerizing an alpha olefin using an iron pentacarbonyl
catalyst.
[0025] The processes of alkylating an alkyl oxy benzene with an
olefin to produce an alkyl oxy benzene, and sulfonating the alkyl
oxy benzene to produce an alkyl oxy benzene sulfonic acid are both
discussed in detail in U.S. Pat. Nos. 5,330,663 and 5,330,664,
which have been incorporated by reference for all purposes. Our
alkylation and sulfonation processes differ only in the olefins
used and reaction time. In our batch alkylation reaction, we need
only about six to eight hours. The preferred sulfonation process is
a falling film process using a charge mole ratio of sulfur trioxide
to alkylphenol of 1.1:1 and a reaction temperature in the range of
from 70.degree. to 100.degree. C., followed by immediate
neutralization.
[0026] A neutralized slurry of alkyl oxy benzene sulfonic acid is
added to a slurry of xylenes, methanol, and calcium hydroxide. The
resulting slurry is then carbonated during which a second slurry of
alkyl oxy benzene sulfonic acid and a second slurry of xylenes,
methanol, and calcium hydroxide are added. After the carbonation,
the material is stripped to remove methanol and water. Lube oil is
then added and the solids removed. The remainder of the solvents
are then stripped off and additional lube oil added to adjust the
product to the final base number.
THE LUBRICATING OIL PRODUCT
[0027] The oil-soluble, highly overbased, alkyl oxy benzene
sulfonate additive compositions produced by the process of this
invention are useful lubricating oil additives imparting detergency
and dispersency properties when added to the lubricating oil
composition employed in the crank case of an internal combustion
engine. Such lubricating oil compositions comprise a major amount
of base oil of lubricating viscosity; and a minor amount of
oil-soluble, highly overbased, alkyl oxy benzene sulfonate additive
compositions. These lubricating oil compositions are useful in
diesel engines, gasoline engines, as well as in marine engines.
[0028] Such lubricating oil compositions employ a finished
lubricating base oil oil of lubricating viscosity which may be
single or multigrade. Multigrade lubricating base oils are prepared
by adding viscosity index (VI) improvers. Typical viscosity index
improvers are polyalkyl methacrylates, ethylene and propylene
copolymers, styrene-diene copolymers, and the like.
[0029] The lubricating base oils used in such compositions may be
mineral oils or synthetic oils of viscosity suitable for use in the
crank case of an internal combustion engine such as gasoline
engines and diesel engines which include marine engines. Crank case
lubricating oils ordinarily have a viscosity of about 1300 cSt at
0.degree. F. to 24 cSt at 210.degree. F. (99.degree. C.). The
lubricating base oils may be derived from synthetic or natural
sources. Mineral oils for use as the base oil in the invention
includes 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, alkylbenzenes of proper viscosity such as
didodecyl benzene, can be used. Useful synthetic esters include
esters of both monocarboxylic acids and polycarboxylic acids as
well as monohydroxy alkenols 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.
[0030] Blends of hydrocarbon oils with synthetic oils are also
useful. For example, blends of 10 to 25 wt. % hydrogenated 1-decene
trimer with 75 to 90 wt. % 150 SUS (100.degree. F.) mineral oil
gives an excellent lubricating base oil.
[0031] In one embodiment, the lubricating oil also has an ashless
dispersant and a zinc dialkyldithiophosphate.
[0032] In another embodiment, the lubricating oil also has a
detergent selected from the group consisting of metal phenates,
metal sulfonates, and metal salicylates.
[0033] Other additives which may be present in the formulation
include rust inhibitors, foam inhibitors, corrosion inhibitors,
metal deactivators, pour point depressants, anti-oxidants, and a
variety of other well-known additives
[0034] More specifically, the following additive components
examples of components that can be favorably employed in
combination with the overbased, alkyl oxy benzene sulfonate of the
present invention
[0035] (1) Metallic detergents: overbased sulfurized alkylphenates,
overbased sulfonates, and overbased salicylates.
[0036] (2) Ashless dispersants: alkenyl succinimides, alkenyl
succinimides modified with other organic compounds, and alkenyl
succinimides modified with boric acid, alkenyl succinic ester.
[0037] (3) Oxidation inhibitors
[0038] 1) Phenol type phenolic) oxidation inhibitors:
4,4'-methylenebis (2,6-di-tert-butylphenol),
4,4'-bis(2,6-di-tert-butylphenol),
4,4'-bis(2-methyl6-tert-butylphenol),
2,2'-(methylenebis(4-methyl6-tert-b- utyl-phenol),
4,4'-butylidenebis(3-methyl-6-tert-butylphenol),
4,4'-isopropylidenebis(2,6-di-tert-butylphenol),
2,2'-methylenebis(4-meth- yl-6-nonylphenol),
2,2'-isobutylidene-bis(4,6-dimethylphenol),
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,6-di-tert-butyl4-methyl- phenol, 2,6-di-tert-butyl4-ethylphenol,
2,4-dimethyl-6-tert-butyl-phenol,
2,6-di-tert-a-dimethylamino-p-cresol,
2,6-di-tert4-(N,N'dimethylaminometh- ylphenol),
4,4'-thiobis(2-methyl-6-tert-butylphenol),
2,2'-thiobis(4-methyl-6-tert-butylphenol),
bis(3-methyl4-hydroxy-5-tert-b- utylbenzyl)-sulfide, and bis
(3,5-di-tert-butyl-4-hydroxybenzyl).
[0039] 2) Diphenylamine type oxidation inhibitor: alkylated
diphenylamine, phenyl-.alpha.-naphthylamine, and alkylated
.alpha.-naphthylamine.
[0040] 3) Other types: metal dithiocarbamate (e.g., zinc
dithiocarbamate), and methylenebis (dibutyldithiocarbamate).
[0041] (4) Rust inhibitors (Anti-rust agents)
[0042] 1) Nonionic polyoxyethylene surface active agents:
[0043] polyoxyethylene lauryl ether, polyoxyethylene higher alcohol
ether, polyoxyethylene nonylphenyl ether, polyoxyethylene
octylphenyl ether, polyoxyethylene octyl stearyl ether,
polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate,
polyoxyethylene sorbitol mono-oleate, and polyethylene glycol
monooleate.
[0044] 2) Other compounds: stearic acid and other fatty acids,
dicarboxilic acids, metal soaps, fatty acid amine salts, metal
salts of heavy sulfonic acid, partial carboxylic acid ester of
polyhydric alcohol, and phosphoric ester.
[0045] (5) Demulsifiers: addition product of alkylphenol and
ethyleneoxide, poloxyethylene alkyl ether, and polyoxyethylene
sorbitane ester.
[0046] (6) Extreme pressure agents (EP agents): zinc
dialkyldithiophosphate (Zn-DTP, primary alkyl type & secondary
alkyl type), sulfurized oils, diphenyl sulfide, methyl
trichlorostearate, chlorinated naphthalene, benzyl iodide,
fluoroalkylpolysiloxane, and lead naphthenate.
[0047] (7) Friction modifiers: fatty alcohol, fatty acid, amine,
borated ester, and other esters
[0048] (8) Multifunctional additives: sulfurized oxymolybdenum
dithiocarbamate, sulfurized oxymolybdenum organo phosphoro
dithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate
amide, amine-molybdenum complex compound, and sulfur-containing
molybdenym complex compound
[0049] (9) Viscosity index improvers: polymethacrylate type
polymers, ethylene-propylene copolymers, styrene-isoprene
copolymers, hydrated styrene-isoprene copolymers, polyisobutylene,
and dispersant type viscosity index improvers.
[0050] (10) Pour point depressants: polymethyl methacrylate
EXAMPLES
[0051] 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.
Comparative Example
Alkylation Using Normal .alpha.-olefins
[0052] A. Preparation of Alkylated Phenols
[0053] High overbased alkyl hydroxy benzene sulfonates were
prepared using an alkylphenol derived by contacting 3.0 moles of
phenol per each mole of a normal C.sub.20 to C.sub.24
.alpha.-olefin mixture using Amberlyst-36 catalyst [a polystyrene
cross-linked sulfonic acid resin having a Hammett acid function
(H.sub.o) of less than -2.2 and an acid number of 5.4
milliequivalents per gram]. Amberlyst-36 resin catalyst is
commercially available from Rohm & Haas, Philadelphia, Pa.
[0054] The olefin mixture had the following olefinic positions,
determined by using a macro program using Nuclear Magnetic
Resonance Spectroscopy (NMR).
1 wt. % Tri- wt. % Alpha wt. % Beta wt. % Internal substituted 89.1
0.5 1.4 0.3
[0055] The alkylation reactions were conducted at 100.degree. C.
using a batch alkylation unit. The reaction time was six hours.
Afterwards, the alkylated phenol was recovered by filtering and
then stripping the excess phenol from the product stream at
400.degree. F. and 1 torr. The recovered alkylphenol products were
analyzed for monoalkyl and dialkyl content and ortho/para
substitution by superfluid chromatography (SFC) and fourier
transform infrared spectroscopy (FT-IR) respectively.
[0056] The results of the SFC analysis are set forth in the table
below:
2 % olefin/parrafin 0.3 wt. % % monoalkylate 86.7 wt. % %
dialkylate 12.6 wt. % % phenol 0.1 wt. %
[0057] The results of the FT-IR analysis for the monoalkylate are
set forth in the table below:
3 % ortho 50.3 wt. % % para 49.7 wt. %
[0058] The alkylphenol was analyzed using gas chromatography and
mass spectrometry. Average positional attachment results for the
C.sub.22 carbon are as follows:
4 P.sub.2 P.sub.3 P.sub.4 P.sub.5 P.sub.6 P.sub.7 P.sub.8 P.sub.9
P.sub.10 P.sub.11 49.84 17.80 9.99 4.65 4.47 3.47 2.95 2.61 2.17
2.04
[0059] B. Sulfonation of Alkylated Phenols
[0060] The alkylated phenol was sulfonated using a falling film
reactor. Reaction conditions were as follows:
[0061] Feed rate of alkylphenol was 4.26 gms/min
[0062] Charge mole ratio of sulfur trioxide to alkylphenol was
1.03:1
[0063] Air to sulfur trioxide ratio was 4:1
[0064] Reaction temperature was 90.degree. C.
[0065] Cyclohexamine analysis for this product indicates that a
sulfonate as Ca value of 3.79 wt. % was obtained.
[0066] C. Neutralization
[0067] 380 grams of alkylphenol sulfonic acids produced above were
immediately neutralized in a stirred beaker containing 320 grams
xylenes, 16 grams methanol, and 32 grams calcium hydroxide.
[0068] D. Overbasing
[0069] 450 grams of xylenes, 90 grams of methanol, and 138.5 grams
of calcium hydroxide were added to a reactor and stirred for five
minutes. A slurry made up of 190.0 grams of alkylhydroxy benzene
sulfonic acid at 3.80 wt. % Ca as sulfonate, 160 grams xylenes, 8
grams methanol, and 16 grams calcium hydroxide, were then added to
the reactor and stirred for 20 minutes. The slurry was heated to
90.degree. F. during the 20 minute stir period. 79 grams of carbon
dioxide was charged to the reactor over 130 minutes. The rate of
addition of the carbon dioxide was gradually reduced from 0.76
grams per minute to 0.25 grams per minute over the carbonation
period. At 75% of the carbon dioxide charge, a second slurry made
up of 190.0 grams of alkylhydroxy benezene sulfonic acid at 3.80
wt. % Ca as sulfonate, 160 grams xylenes, 8 grams methanol, and 16
grams calcium hydroxide was added. At 80% of the carbon dioxide
charge, a slurry of 56 grams xylenes, 13 grams methanol, and 35.5
grams calcium hydroxide was added.
[0070] At the end of carbonation, the reactor was equipped with a
condenser for stripping and the temperature was ramped to
200.degree. F. over two hours. At 200.degree. F., the temperature
was then ramped to 270.degree. F. over 30 minutes. At 270.degree.
F., 215 grams of 100 Neutral oil was added and the entire batch was
then filtered through a Buchner filter. The filtrate was then
stripped to 400.degree. F. at 40 mm Hg vacuum. The base number was
then measured with a resulting number of 318. An additional 45
grams of 100 Neutral oil was added to adjust the base number to
312.5.
[0071] The final product had a viscosity that was too viscous to
measure at 100.degree. C. at a TBN of 312.5. It had 22.37% of the
alkyl group of the sulfonate attached at the 4-position and higher
positions of the alkyl group.
Example 1
Alkylation Using Isomerized Olefins
[0072] The procedures of the Comparative Example were repeated
using a C.sub.20 to C.sub.24 olefin mixture isomerized by using
iron pentacarbonyl isomerization. This isomerization process is
known in the literature, and is disclosed in T. A. Manuel, Journal
of Organic Chemistry, 27, 3941 (1962). The olefin mixture had the
following olefinic positions, determined by using a macro program
using NMR.
5 wt. % Alpha wt. % Beta wt. % Internal wt. % Tri-substituted 0.6
13.6 97 2.4
[0073] The alkylphenol was analyzed using gas chromatography and
mass spectrometry. Average positional attachment results for the
C.sub.22 carbon are as follows:
6 P.sub.2 P.sub.3 P.sub.4 P.sub.5 P.sub.6 P.sub.7 P.sub.8 P.sub.9
P.sub.10 P.sub.11 30.23 12.52 7.92 7.57 8.05 7.05 6.74 6.18 6.61
7.11
[0074] The final product had a viscosity of 581 cSt at 100.degree.
C. at a TBN of 300. It had 49.33% of the alkyl group of the
sulfonate attached at 4-position and higher positions of the alkyl
group.
Example 2
Alkylation Using Polyalpha Olefins
[0075] The procedures of the Comparative Example were repeated
using a polyalpha olefin derived from C.sub.10 dimer. The polyalpha
olefin had the following olefinic positions, determined by using a
macro program using NMR.
7 wt. % Alpha wt. % Beta wt. % Internal wt. % Tri-substituted 14.0
13.4 29.8 56.0
[0076] The alkylphenol was analyzed using gas chromatography and
mass spectrometry. Average positional attachment results for the
C.sub.22 carbon are as follows:
8 P.sub.2 P.sub.3 P.sub.4 P.sub.5 P.sub.6 P.sub.7 P.sub.8 P.sub.9
P.sub.10 P.sub.11 48.0 16.0 7.6 7.2 5.9 5.2 4.5 3.4 2.3 0.0
[0077] The final product had a viscosity of 109 cSt at 100.degree.
C. at a TBN of 296. It had 28.45% of the alkyl group of the
sulfonate attached at 4-position and higher positions of the alkyl
group.
Comparison to Commercial Metal-containing Detergents
[0078] Results of experiments for comparing the overbased phenoxy
sulfonate of the invention with commercially available
metal-containing detergents are shown below
[0079] Oxidation Stability
[0080] Test method: according to JIS K-2514
[0081] Tested detergents:
[0082] Example 1: Overbased phenoxy sulfonate of invention which is
described in Example 1 of Specification
[0083] Phenate I: Commercially available overbased phenate
[0084] Phenate II: Another commercially available overbased
phenate
[0085] Sulfonate: Commercially available overbased sulfonate
[0086] Salicylate I: Commercially available overbased
salicylate
[0087] Salicylate II: Another commercially available overbased
salicylate
[0088] Oil for test: TBN 33 in SAE #40
[0089] Test conditions: heated at 165.5.degree. C. for 72 hours
[0090] Results: set forth in the following table
9 Metal-Containing Ratio of Viscosity (40.degree.)C.) Detergent
(Heated/Unheated) Example 1 1.06 Phenate I 1.25 Phenate II 1.22
Sulfonate 1.39 Salicylate I 1.09 Salicylate II 1.42
[0091] The above results show the improved oxidation stability of
the phenoxy sulfonate of the invention.
[0092] Detergency at Elevated Temperature
[0093] Test method: Hot tube test
[0094] Oil for test: TBN 33 in SAE #40
[0095] Test conditions: 330.degree. C., 16 hours
[0096] Results: set forth in the following table
10 Metal-Containing Detergent Laquer rating (10 = Clear)) Example 1
6.0 Phenate I 0 Phenate II 6.0 Sulfonate 0 Salicylate I 6.0
Salicylate II 6.0
[0097] The above results show the improved detergency of the
phenoxy sulfonate of the invention at an elevated temperature
[0098] Thermal Stability
[0099] Test method: Panel coker test
[0100] Oil for test: TBN 33 in SAE #40
[0101] Test conditions: 320.degree. C., 3 hours
[0102] Results: set forth in the following table
11 Metal-Containing Detergent Deposit (mg) Example 1 40 Phenate I
10 Phenate II -- Sulfonate 430 Salicylate I 155 Salicylate II
55
[0103] The above results show the improved thermal stability of the
penoxy sulfonate of the invention.
[0104] Friction Coefficient
[0105] Oil for test:
[0106] SAE 10W30 oil is prepared by compounding a succinimide
ashless dispersant, a low overbased calcium sulfonate, zinc
dialkyldithiophosphate, and a viscosity index improver into 150
neutral oil. To the compounded oil is added the metal-containing
detergent in an amount corresponding to TBN 10.
[0107] Results: set forth in the following table
12 Metal-Containing Friction Coefficient Detergent 80.degree. C.
120.degree. C. Example 1 0.100 0.087 Phenate I 0.163 0.157 Phenate
II -- -- Sulfonate 0.137 0.132 Salicylate I -- -- Salicylate II --
--
[0108] The above results show the reduction of friction coefficient
proved by the phenoxy sulfonate of the invention.
[0109] Stability in Water
[0110] Test method: ASTM D-2619 (modified)
[0111] Oil for test: TBN 33 in SAE #40
[0112] Test conditions: 100 g of the test oil (its TBN is
previously determined) and 5 g of distilled water are placed in a
pressure-resistant bottle. The bottle is placed in an air
thermostat at 93.degree. C., for 24 hrs. under the condition that
the bottle is rotated with upside down at 5 r.p.m., for hydrolyzing
the test oil.
[0113] The hydrolyzed test oil is then determined for its TBN.
Decrease of TBN per the original TBN is calculated.
[0114] Results: set forth in the following table.
13 Metal-Containing Detergent Decrease of TBN (%) Example 1 1
Phenate I 70 Phenate II 20 Sulfonate 30 Salicylate I 1 Salicylate
II 6
[0115] The above results show the stability in water of the phenoxy
sulfonate of the invention.
Examples of Additive Packages
[0116] The following wt. % is based on the amount of an active
component, namely, with neither process oil nor diluent oil. The
phenoxy sulfonate employed is that described in Example 1.
14 I. Marine Diesel Engine Oils 1) Phenoxy sulfonate 65.0 wt. %
Primary alkyl Zn-DTP 5.9 wt. % Diluent oil 29.1 wt. % 2) Phenoxy
sulfonate 64.0 wt. % Alkenylsuccinimide ashless dispersant 6.3 wt.
% Diluent oil 29.7 wt. % 3) Phenoxy sulfonate 59.0 wt. % Primary
alkyl Zn-DTP 5.4 wt. % Alkenylsuccinimide ashless dispersant 5.9
wt. % Diluent oil 29.7 wt. % 4) Phenoxy sulfonate 63.6 wt. % Phenol
type oxidation inhibitor 9.1 wt. % Diluent oil 27.3 wt. % 5)
Phenoxy sulfonate 53.5 wt. % Alkylated diphenylamine-type 16.3 wt.
% oxidation inhibitor Diluent oil 30.2 wt. % 6) Phenoxy sulfonate
63.6 wt. % Phenol-type oxidation inhibitor 4.5 wt. % Alkylated
diphenylamine-type 4.6 wt. % oxidation inhibitor Diluent oil 27.3
wt. % 7) Phenoxy sulfonate 59.5 wt. % Primary alkyl Zn-DTP 5.4 wt.
% Phenol-type oxidation inhibitor 5.0 wt. % Diluent oil 30.0 wt. %
8) Phenoxy sulfonate 58.3 wt. % Alkenylsuccinimide ashless
dispersant 5.8 wt. % Alkylated diphenylamine-type 8.3 wt. %
oxidation inhibitor Diluent oil 27.5 wt. % 9) Phenoxy sulfonate
57.0 wt. % Primary alkyl Zn-DTP 5.2 wt. % Alkenylsuccinic ester
ashless dispersant 5.7 wt. % Phenol-type oxidation inhibitor 2.1
wt. % Alkylated diphenylamine-type 2.0 wt. % oxidation inhibitor
Diluent oil 28.0 wt. % 10) Phenoxy sulfonate 46.2 wt. % Overbased
sulfurized alkylphenate 20.8 wt. % Diluent oil 44.0 wt. % 11)
Phenoxy sulfonate 37.0 wt. % Overbased sulfurized alkylsalicylate
28.0 wt. % Diluent oil 35.0 wt. % 12) Phenoxy sulfonate 58.9 wt. %
Overbased sulfonate 4.7 wt. % Primary alkyl Zn-DTP 6.5 wt. %
Diluent oil 29.9 wt. % 13) Phenoxy sulfonate 48.3 wt. % Overbased
sulfurized alkylphenate 14.7 wt. % Primary alkyl Zn-DTP 6.0 wt. %
Diluent oil 31.0 wt. % 14) Phenoxy sulfonate 40.8 wt. % Overbased
sulfurized phenate 17.5 wt. % Alkenylsuccinimide ashless dispersant
6.7 wt. % Diluent oil 35.0 wt. % 15) Phenoxy sulfonate 45.9 wt. %
Overbased sulfurized phenate 11.5 wt. % Alkenylsuccinic ester
ashless disersant 4.9 wt. % Primary alkyl Zn-DTP 4.9 wt. % Diluent
oil 32.8 wt. % 16) Phenoxy sulfonate 63.9 wt. % Overbased
sulfurized alkylphenate 3.3 wt. % Phenol type oxidation inhibitor
1.1 wt. % Alkylated diphenylamine-type 1.0 wt. % oxidation
inhibitor Diluent oil 30.7 wt. % 17) Phenoxy sulfonate 51.6 wt. %
Overbased sulfurized alkylphenate 5.7 wt. % Primary alkyl Zn-DTP
3.3 wt. % Alkenylsuccinimide ashless dispersant 4.1 wt. % Alkylated
diphenylamine-type 1.6 wt. % oxidation inhibitor Diluent oil 33.7
wt. % 18) Phenoxy sulfonate 53.4 wt. % Primary alkyl Zn-DTP 3.4 wt.
% Alkenylsuccinimide ashless dispersant 5.7 wt. % Demulsifier 5.7
wt. % Diluent oil 31.8 wt. % 19) Phenoxy sulfonate 47.0 wt. %
Overbased sulfurized alkylphenate 16.0 wt. % Primary alkyl Zn-DTP
2.5 wt. % Alkenylsuccinimide ashless dispersant 3.4 wt. %
Demulsifier 2.5 wt. % Diluent oil 28.6 wt. % II. Motor Car Engine
Oils 1) Phenoxy sulfonate 25.3 wt. % Alkenylsuccinimide ashless
dispersant 35.9 wt. % Primary alkyl Zn-DTP 11.2 wt. % Diluent oil
27.6 wt. % 2) Phenoxy sulfonate 21.1 wt. % Overbased sulfonate 8.6
wt. % Alkenylsuccinimide ashless dispersant 30.1 wt. % Primary
alkyl Zn-DTP 9.7 wt. % Diluent oil 30.5 wt. % 3) Phenoxy sulfonate
18.9 wt. % Alkenylsuccinimide ashless dispersant 39.6 wt. %
Secondary alkyl Zn-DTP 6.3 wt. % Dithiocarbamate type 4.2 wt. %
oxidation inhibitor Diluent oil 31.0 wt. % 4) Phenoxy sulfonate
14.9 wt. % Overbased sulfurized alkylphenate 3.8 wt. %
Alkenylsuccinimide ashless dispersant 35.1 wt. % Secondary alkyl
Zn-DTP 6.4 wt. % Phenol type oxidation inhibitor 4.3 wt. % Diluent
oil 35.5 wt. % 5) Phenoxy sulfonate 20.0 wt. % Alkenylsuccinimide
ashless dispersant 32.1 wt. % Secondary alkyl Zn-DTP 7.1 wt. %
Dithiocarbamate type anti-wear agent 3.6 wt. % Diluent oil 37.2 wt.
% 6) Phenoxy sulfonate 7.4 wt. % Overbased sulfurized alkylphenate
8.4 wt. % Basic sulfonate 3.7 wt. % Succinimide ashless dispersant
31.6 wt. % Secondary alkyl Zn-DTP 5.8 wt. % Molybdenum-containing
anti-wear agent 3.7 wt. % Diluent oil 39.4 wt. % 7) Phenoxy
sulfonate 17.7 wt. % Alkenylsuccinimide ashless dispersant 28.7 wt.
% Primary alkyl Zn-DTP 3.4 wt. % Secondary alkyl Zn-DTP 5.0 wt. %
Alkylated diphenylamine-type 5.7 wt. % oxidation inhibitor
Dithiocarbamate type anti-wear agent 0.9 wt. % Diluent oil 38.6 wt.
% 8) Phenoxy sulfonate 12.9 wt. % Alkenylsuccinimide ashless
dispersant 37.9 wt. % Secondary alkyl Zn-DTP 8.2 wt. % Phenol type
oxidation inhibitor 1.0 wt. % Alkylated diphenylamine-type 4.1 wt.
% oxidation inhibitor Dithiocarbamate type anti-wear agent 1.0 wt.
% Demulsifier 0.9 wt. % Boron-containing friction modifier 2.1 wt.
% Diluent 31.9 wt. % III. Hydraulic Oils 1) Phenoxy sulfonate 4.6
wt. % Primary alkyl Zn-DTP 64.5 wt. % Phenol type oxidation
inhibitor 6.6 wt. % Phosphorous-containing 4.9 wt. % extreme
pressure agent Triazol type corrosion inhibitor 3.8 wt. %
Demulsifier 3.3 wt. % Nonionic anti-rust agent 3.3 wt. % Diluent
oil 9.0 wt. % 2) Phenoxy sulfonate 2.3 wt. % Basic sulfurized
alkylphenate 2.5 wt. % Primary alkyl Zn-DTP 49.6 wt. % Phenol type
oxidation inhibitor 7.3 wt. % Sulfur-containing extreme 6.0 wt. %
pressure agent Triazol type corrosion inhibitor 3.4 wt. %
Demulsifier 5.0 wt. % Nonionic anti-rust agent 3.0 wt. % Diluent
oil 13.9 wt. % 3) Pehonoxy sulfonate 12.2 wt. % Phenol type
oxidation inhibitor 14.8 wt. % Diphenylamine type 7.4 wt. %
oxidation inhibitor Sulfur-containing 4.5 wt. % extreme pressure
agent Phosphorous-containing 39.2 wt. % extreme pressure agent
Triazol type corrosion inhibitor 1.0 wt. % Demulsifier 7.0 wt. %
Nonionic anti-rust agent 4.5 wt. % Diluent oil 9.4 wt. % 4) Phenoxy
sulfonate 5.5 wt. % Overbased salicylate 3.7 wt. % Phenol type
oxidation inhibitor 13.5 wt. % Diphenylamine type 8.2 wt. %
oxidation inhibitor Sulfur-containing extreme 4.5 wt. % pressure
agent Phosphorous-containing 42.7 wt. % extreme pressure agent
Triazol type corrosion inhibitor 1.2 wt. % Demulsifier 6.5 wt. %
Nonionic anti-rust agent 4.3 wt. % Diluent oil 6.9 wt. % IV.
Transmission Hydraulic Fluids 1) Phenoxy sulfonate 35.9 wt. %
Primary alkyl Zn-DTP 20.9 wt. % Polyol type friction modifier 17.9
wt. % Sulfur-containing extreme 5.8 wt. % pressure agent Diluent
oil 19.5 wt. % 2) Phenoxy sulfonate 28.8 wt. % Basic sulfonate 11.3
wt. % Primary alkyl Zn-DTP 16.7 wt. % Amide type friction modifier
13.9 wt. % Sulfur-containing extreme 6.0 wt. % pressure agent
Diluent oil 23.3 wt. % 3) Phenoxy sulfonate 32.2 wt. % Primary
alkyl Zn-DTP 18.9 wt. % Alkenylsuccinimide ashless dispersant 0.5
wt. % Amide type friction modifier 10.4 wt. % Ester type friction
modifier 13.9 wt. % Phosphorous, Sulfur-containing 6.3 wt. %
extreme pressure agent Diluent oil 17.8 wt. % 4) Phenoxy sulfonate
23.6 wt. % Basic sulfonate 10.1 wt. % Overbased salicylate 2.4 wt.
% Primary aikyl Zn-DTP 15.2 wt. % Polyol type friction modifier 0.4
wt. % Amide type friction modifier 8.4 wt. % Phosphorous,
Sulfur-containing 5.1 wt. % extreme pressure agent Diluent oil 23.6
wt. %
[0117] 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.
* * * * *