U.S. patent application number 11/813112 was filed with the patent office on 2008-08-28 for emulsion composition.
This patent application is currently assigned to THE LUBRIZOL CORPORATION. Invention is credited to Stephen J. Cook, David Hobson, Alexandra Mayhew, Gurumayum Shachi Dayal Sharma, Sarah J. Startin.
Application Number | 20080207473 11/813112 |
Document ID | / |
Family ID | 36263754 |
Filed Date | 2008-08-28 |
United States Patent
Application |
20080207473 |
Kind Code |
A1 |
Startin; Sarah J. ; et
al. |
August 28, 2008 |
Emulsion Composition
Abstract
The present invention provides an emulsion composition
containing (a) a first phase with (i) an oil soluble inert medium;
and (ii) an emulsifier capable of forming a water-in-oil emulsion;
and (b) a second phase with (i) a metal base; (ii) an aqueous
medium; and (iii) optionally a compound containing two or more
hydroxyl groups, wherein a base in the form of an alkali metal or
an alkaline earth metal oxide, hydroxide, carbonate, bicarbonate;
or combinations thereof; and wherein the emulsion composition has a
flow rate through a 45 .mu.m filter of more than 8 ml/min in a
filterability test carried out at ambient temperature and 45 kPa
applied vacuum; wherein the filter has diameter of 5 cm and a mesh
size of about 45 .mu.m; and wherein the oil soluble inert medium in
the filtration test is an oil of lubricating viscosity of a SAE 50
base oil. The invention further provides a method of preparing the
emulsion composition and its use in a marine engine.
Inventors: |
Startin; Sarah J.;
(Ashbourne, GB) ; Sharma; Gurumayum Shachi Dayal;
(Derby, GB) ; Hobson; David; (Wirksworth, GB)
; Mayhew; Alexandra; (Wirksworth, GB) ; Cook;
Stephen J.; (Belper, GB) |
Correspondence
Address: |
THE LUBRIZOL CORPORATION;ATTN: DOCKET CLERK, PATENT DEPT.
29400 LAKELAND BLVD.
WICKLIFFE
OH
44092
US
|
Assignee: |
THE LUBRIZOL CORPORATION
Wickliffe
OH
|
Family ID: |
36263754 |
Appl. No.: |
11/813112 |
Filed: |
January 10, 2006 |
PCT Filed: |
January 10, 2006 |
PCT NO: |
PCT/US06/00827 |
371 Date: |
August 30, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60643681 |
Jan 13, 2005 |
|
|
|
Current U.S.
Class: |
508/180 ;
508/154 |
Current CPC
Class: |
C10M 2207/127 20130101;
C10L 1/328 20130101; C10N 2010/02 20130101; C10N 2030/04 20130101;
C10N 2010/04 20130101; C10M 2201/02 20130101; C10M 2207/022
20130101; C10M 2215/086 20130101; C10M 2201/062 20130101; C10M
2207/123 20130101; C10M 173/00 20130101; C10N 2040/252 20200501;
C10N 2030/12 20130101; C10M 2207/129 20130101; C10M 2215/28
20130101; C10N 2030/06 20130101; C10M 2207/121 20130101; C10M
2207/125 20130101; C10N 2020/01 20200501 |
Class at
Publication: |
508/180 ;
508/154 |
International
Class: |
C10M 103/00 20060101
C10M103/00 |
Claims
1. An emulsion composition comprising: (a) a first phase
comprising: (i) an oil soluble inert medium; and (ii) an emulsifier
capable of forming a water-in-oil emulsion; and (b) a second phase
comprises: (i) a metal base; (ii) an aqueous medium; and (iii)
optionally a compound containing two or more hydroxyl groups,
wherein a base in the form of an alkali metal or an alkaline earth
metal oxide, hydroxide, carbonate, bicarbonate; or combinations
thereof; and wherein the emulsion composition has a flow rate
through a 45 .mu.m filter of more than 8 ml/min in a filterability
test carried out at ambient temperature and 45 kPa applied vacuum;
wherein the filter has diameter of 5 cm and a mesh size of about 45
.mu.m; and wherein the oil soluble inert medium in the filtration
test is an oil of lubricating viscosity of a SAE 50 base oil.
2. The emulsion composition of claim 1, wherein the oil soluble
inert medium is an oil of lubricating viscosity.
3. The emulsion composition of claim 3, wherein the oil of
lubricating viscosity has a SAE grade of 30-50.
4. The emulsion composition of claim 1, wherein the emulsifier is a
hydrocarbon lubricant-soluble hydrocarbyl substituted carboxylic
acid acylating agent.
5. The emulsion composition of claim 4, wherein the emulsifier is a
hydrocarbyl-substituted succinic acid or anhydride.
6. The emulsion composition of claim 1, wherein the emulsifier has
a HLB of 1 to 8.
7. The emulsion composition of claim 1, wherein the metal base has
a total surface area of 2 m.sup.2g.sup.-1 to 10
m.sup.2g.sup.-1.
8. The emulsion composition of claim 1, wherein the metal of the
metal base is calcium.
9. The emulsion composition of claim 1, wherein the metal base is a
calcium oxide or hydroxide.
10. The emulsion composition of claim 1 further comprising the
compound containing two or more hydroxyl groups.
11. The emulsion composition of claim 10, wherein the compound
containing two or more hydroxyl groups has 2 to 8 hydroxyl
groups.
12. The emulsion composition of claim 11, wherein the compound
containing two or more hydroxyl groups is ethylene glycol,
diethylene glycol, triethylene glycol, glycerol, sorbitol,
pentaerythritol, dipentaerythritol or mixtures thereof.
13. The emulsion composition of claim 1 further comprising a
detergent, a dispersant or mixtures thereof.
14. An emulsion composition comprising: (a) a first phase
comprising: (i) 50 wt % to 97 wt % of an oil soluble inert medium;
and (ii) 0.05 wt % to 10 wt % of an emulsifier capable of forming a
water-in-oil emulsion; and (b) a second phase comprises: (i) a
metal base; (ii) an aqueous medium; (iii) 0.05 wt % to 5 wt % of a
compound containing two or more hydroxyl groups; and (iv) 0.5 wt %
to 10 wt % of at least one other performance additive, wherein a
base in the form of an alkali metal or an alkaline earth metal
oxide, hydroxide, carbonate, bicarbonate; or combinations thereof;
and wherein the emulsion composition has a flow rate through a 45
.mu.m filter of more than 8 ml/min in a filterability test carried
out at ambient temperature and 45 kPa applied vacuum; wherein the
filter has diameter of 5 cm and a mesh size of about 45 .mu.m; and
wherein the oil soluble inert medium in the filtration test is an
oil of lubricating viscosity of a SAE 50 base oil.
15. A method for lubricating an internal combustion engine,
comprising supplying thereto a lubricant comprising the emulsion
composition of claim 1.
16. The method of claim 15, wherein the internal combustion engine
is a 2-stroke or a 4-stroke marine diesel engine.
Description
CROSS REFERENCE
[0001] This application claims priority from U.S. Patent
Application Ser. No. 60/643,681 filed on Jan. 13, 2005.
FIELD OF INVENTION
[0002] The present invention relates to an emulsion composition
containing an inert medium, a metal base, an emulsifier, an aqueous
base and optionally a compound containing 2 or more hydroxyl
groups. The invention further discloses the use of an emulsion
composition in an internal combustion engine.
BACKGROUND OF THE INVENTION
[0003] A variety of lubricant oils are available having various
total base numbers. One reason for having a total base number above
zero in a lubricant is that acidic products are more likely to
cause corrosion and wear to metal parts of a device than bases,
which tend not to be involved in corrosion. Thus, lubricants are
formulated with sufficient excess base that over their intended
lifetime, they remain neutral or slightly basic.
[0004] One particular use of a lubricant with a high total base
number is in marine diesel applications which economically burn
residual fuels with a sulphur content up to about 4.5 weight
percent. Due to the high amount of sulphur containing species in
the economical residual fuel, the combustion products include high
amount of acidic SO.sub.x which causes additional wear to the
cylinder wall and the rings of the piston. A solution to this
lubrication/corrosion problem caused by the SO.sub.x is to include
excess base in the lubricant oil so that the SO.sub.x is converted
to a metal salt of the acid, which has less tendency to cause
corrosion or wear. In many marine diesel applications, the cylinder
oil is injected near the rings of the piston on a continual basis
to provide both continued lubrication and replace the base lost to
neutralisation. In these applications, the cylinder lubricant is
continuously consumed rather than returned to a sump. The marine
diesel lubricant also needs cleanliness, spreadability, corrosive
wear resistance and filterability.
[0005] PCT Application 03/044138 A2 (Cook et al.) discloses a
lubricant composition containing (a) at least one emulsifier
capable of forming a water in oil emulsion, (b) a non-borated base
that at least 1 TBN to said lubricant and at least 10 wt. % of the
base is insoluble in the oil insoluble solvent. The base contains a
metal selected from potassium, sodium, calcium, magnesium, lithium
or aluminum and a counter-ion selected from a hydroxide, a
carbonate, a bicarbonate, a C.sub.1-C.sub.5 organic acid; an oxide;
ammonia; an amine, a guanidine carbonate, urea; or other organic
nitrogen compound which generates ammonia on ignition, or
combinations thereof.
[0006] U.S. Pat. No. 6,533,829 discloses a stabilised liquid
hydrocarbon fuel composition containing an alcohol with 5 to 10
carbon atoms, a carboxylic amide containing 5 to 10 carbon atoms
present at 0.5 to 3 parts by weight relative to the amount of
alcohol; and a carboxylic acid containing 5 to 10 carbon atoms
present at 3 to 10 parts by weight relative to the amount of
alcohol.
[0007] U.S. Pat. No. 6,533,830 discloses a fuel or lubricant
composition containing a polyalkyene alcohol polyalkoxylate.
[0008] It would be desirable to have an emulsion composition with
at least one property from acceptable cleanliness, acceptable
spreadability, acceptable corrosive wear resistance and
acceptable/improved filterability. The present invention provides
an emulsion composition with at least one property from acceptable
cleanliness, acceptable spreadability, acceptable corrosive wear
resistance and acceptable/improved filterability.
SUMMARY OF THE INVENTION
[0009] The present invention provides an emulsion composition
comprising: (a) a first phase comprising: (i) an oil soluble inert
medium; and (ii) an emulsifier capable of forming a water-in-oil
emulsion; and (b) a second phase comprises: (i) a metal base; (ii)
an aqueous medium; and (iii) optionally a compound containing two
or more hydroxyl groups, wherein a base in the form of an alkali
metal or an alkaline earth metal oxide, hydroxide, carbonate,
bicarbonate; or combinations thereof; and wherein the emulsion
composition has a flow rate through a 45 .mu.m filter of more than
8 ml/min in a filterability test carried out at ambient temperature
and 45 kPa applied vacuum; wherein the filter has diameter of 5 cm
and a mesh size of about 45 .mu.m; and wherein the oil soluble
inert medium in the filtration test is an oil of lubricating
viscosity of a SAE 50 base oil.
[0010] In one embodiment, the emulsion composition comprises: (a) a
first phase comprising: (i) an oil soluble inert medium; and (ii)
an emulsifier capable of forming a water-in-oil emulsion; and (b) a
second phase comprises: (i) a metal base; (ii) an aqueous medium;
(iii) a compound containing two or more hydroxyl groups, wherein a
base in the form of an alkali metal or an alkaline earth metal
oxide, hydroxide, carbonate, bicarbonate; or combinations thereof;
and wherein the emulsion composition has a flow rate through a 45
.mu.m filter of more than 8 ml/min in a filterability test carried
out at ambient temperature and 45 kPa applied vacuum; wherein the
filter has diameter of 5 cm and a mesh size of about 45 .mu.m; and
wherein the oil soluble inert medium in the filtration test is an
oil of lubricating viscosity of a SAE 50 base oil.
DETAILED DESCRIPTION OF THE INVENTION
[0011] In one embodiment, the present invention provides an
emulsion composition comprising:
[0012] (a) a first phase comprising: [0013] (i) an oil soluble
inert medium; and [0014] (ii) an emulsifier capable of forming a
water-in-oil emulsion; and
[0015] (b) a second phase comprises: [0016] (i) a metal base;
[0017] (ii) an aqueous medium; and [0018] (iii) optionally a
compound containing two or more hydroxyl groups, wherein a base in
the form of an alkali metal or an alkaline earth metal oxide,
hydroxide, carbonate, bicarbonate; or combinations thereof; and
wherein the emulsion composition has a flow rate through a 45 .mu.m
filter of more than 8 ml/min in a filterability test carried out at
ambient temperature (e.g. 20.degree. C. to 25.degree. C.) and 45
kPa applied vacuum; wherein the filter has diameter of 5 cm and a
mesh size of about 45 .mu.m; and wherein the oil soluble inert
medium in the filtration test is an oil of lubricating viscosity of
a SAE 50 base oil.
[0019] In one embodiment, the emulsion composition comprises:
[0020] (a) a first phase comprising: [0021] (i) an oil soluble
inert medium; and [0022] (ii) an emulsifier capable of forming a
water-in-oil emulsion; and
[0023] (b) a second phase comprises: [0024] (i) a metal base;
[0025] (ii) an aqueous medium; [0026] (iii) a compound containing
two or more hydroxyl groups; and wherein a base in the form of an
alkali metal or an alkaline earth metal oxide, hydroxide,
carbonate, bicarbonate; or combinations thereof; and wherein the
emulsion composition has a flow rate through a 45 .mu.m filter of
more than 8 ml/min in a filterability test carried out at ambient
temperature and 45 kPa applied vacuum; wherein the filter has
diameter of 5 cm and a mesh size of about 45 .mu.m; and wherein the
oil soluble inert medium in the filtration test is an oil of
lubricating viscosity of a SAE 50 base oil.
[0027] In several embodiments, the emulsion composition has a flow
rate through a 45 .mu.m filter of 9 ml/min or more in the
filterability test, 10 ml/min or more in the filterability test or
11 ml/min or more in the filterability test. Examples of ranges of
suitable flow rate include 8.5 ml/min to 50 ml/min, 9.5 ml/min to
40 ml/min or 10.5 ml/min to 30 ml/min.
[0028] In one embodiment, the filterability test has a second phase
of the emulsion composition containing a solids content of a metal
base from 15 wt % to 25 wt %.
[0029] In one embodiment, the filterability test as described above
is replaced by measuring the Theological properties of the metal
base during dewatering. The Theological properties are measured
using a Bohlin Instruments Gemini.TM. Rheometer. The methodology of
the test is described in the Example section and the results
obtained are the length of time required for the formation of a
filter cake. Generally, a filter cake forms when the metal base
aggregates. The methodology of the Bohlin Instruments Gemini.TM.
Rheometer required the metal base to be suspended in water rather
than in the emulsion composition. Generally, the Gemini.TM.
Rheometer is operated at ambient temperature.
[0030] In several embodiments, the length of time required for the
metal base to form of a filter cake is at least 60 seconds (s), or
at least 65 s or at least 70 s. Examples of ranges time required
for the formation of a filter cake include 62 s to 150 s, or 68 s
to 130 s or 75 s to 110 s.
[0031] In several embodiments, the emulsion composition is a water
in oil composition with a wt % ratio of the first phase relative to
the second phase of at least 51 to 49, or at least 55 to 45, or at
least 60 to 40, or at least 65 to 35 or at least 70 to 30.
[0032] The emulsion composition when employed in an internal
combustion engine in several embodiments has a total base number
(TBN) of at least 1, at least 5, at least 10 or at least 30 mg
KOH/g.
[0033] The emulsion composition when employed in a marine diesel
combustion engine in several embodiments has a total base number
(TBN) of at least 5, at least 10, at least 20 or at least 30.
The First Phase
Oil Soluble Inert Medium
[0034] The first phase of the invention includes an oil soluble
inert medium. The oil soluble inert medium includes a liquid fuel
or an oil of lubricating viscosity.
[0035] The inert oil medium is present in several embodiments from
40 wt % to 99.9 wt %, or from 50 wt % to 97 wt %, or from 55 wt %
to 95 wt %, or from 60 wt % to 90 wt % of the emulsion
composition.
Oil of Lubricating Viscosity
[0036] In one embodiment, the emulsion composition includes natural
or synthetic oils of lubricating viscosity, oil derived from
hydrocracking, hydrogenation, hydrofinishing, unrefined, refined
and re-refined oils or mixtures thereof. In several embodiments,
the oil of lubricating viscosity has a SAE grade of 20-70, 30-50 or
40-60.
[0037] Natural oils include animal oils, vegetable oils, mineral
oils or mixtures thereof. Synthetic oils include a hydrocarbon oil,
a silicon-based oil, a liquid esters of phosphorus-containing acid.
Synthetic oils may be produced by Fischer-Tropsch reactions and
typically may be hydroisomerised Fischer-Tropsch hydrocarbons or
waxes.
[0038] Oils of lubricating viscosity may also be defined as
specified in the American Petroleum Institute (API) Base Oil
Interchangeability Guidelines. In several embodiments the oil of
lubricating viscosity comprises an API Group I, II, III, IV, V, VI
or mixtures thereof, or an API Group I, II, III or mixtures
thereof. If the oil of lubricating viscosity is an API Group II,
III, IV, V or VI oil there may be up to 40 wt % or up to a maximum
of 5 wt % of the lubricating oil an API Group I oil.
Liquid Fuel
[0039] In one embodiment, the emulsion composition includes a
liquid fuel that is normally a liquid at ambient conditions. The
liquid fuel includes a hydrocarbon fuel, a nonhydrocarbon fuel, or
a mixture thereof. The hydrocarbon fuel may be a petroleum
distillate including a gasoline as defined by ASTM (American
Society for Testing and Materials) specification D4814 or a diesel
fuel as defined by ASTM specification D975.
[0040] In one embodiment, the liquid fuel is a gasoline, and in
another embodiment, the liquid fuel is a gasohol (i.e., gasoline
alcohol mixture), and in another embodiment the liquid fuel is a
diesel fuel. The hydrocarbon fuel includes a hydrocarbon prepared
by a gas to liquid process, for example, Fischer-Tropsch. The
nonhydrocarbon fuel includes an oxygen containing composition,
often referred to as an oxygenate. The nonhydrocarbon fuel includes
a monohydric alcohol, an ether, a ketone, an ester of a carboxylic
acid, a nitroalkane, or a mixture thereof. Examples of the
nonhydrocarbon fuel include methanol, ethanol, methyl t-butyl
ether, methyl ethyl ketone, transesterified oils and/or fats from
plants and animals such as rapeseed methyl ester and soybean methyl
ester, and nitromethane. Examples of mixtures of the hydrocarbon
and the nonhydrocarbon fuel include gasoline and methanol and/or
ethanol, diesel fuel and ethanol, and diesel fuel and a
transesterified plant oil such as rapeseed methyl ester.
Emulsifier
[0041] The first phase includes an emulsifier capable of forming a
water-in-oil emulsion or mixtures thereof. The emulsifier is
present in one embodiment from 0.01 wt % to 20 wt %, in another
embodiment from 0.05 wt % to 10 wt %, in another embodiment 0.1 wt
% to 5 wt % and in another embodiment from 0.2 wt % to 3 wt % of
the emulsion composition.
[0042] The emulsifier includes a hydrocarbon lubricant-soluble
hydrocarbyl substituted carboxylic acid acylating agent. The
hydrocarbyl substituted carboxylic acid acylating agent emulsifier
may be produced by reacting a hydrocarbyl substituted carboxylic
acid acylating agent with ammonia or an amine, the hydrocarbyl
substituent of said acylating agent having 50 to 500 carbon atoms;
(ii) an ionic or a nonionic compound having a hydrophilic
lipophilic balance (HLB) of 1 to 30 in another embodiment less than
10, in another embodiment 1 to 8, and in yet another embodiment 2.5
to 6. Those skilled in the art will appreciate that combinations of
surfactants may be used with individual HLB values outside of the
given ranges provided that the composition of the final emulsifier
blend is within these ranges.
[0043] The hydrocarbyl-substituted carboxylic acid acylating agent
for the hydrocarbon lubricant-soluble product (i) may be a
carboxylic acid or a reactive equivalent of such acid. The reactive
equivalent may be an acid halide, anhydride, or ester, including
partial esters and the like. The hydrocarbyl substituent for the
carboxylic acid acylating agent may contain from 50 to 300 or 500
carbon atoms, and in another embodiment 60 to 200 carbon atoms. In
one embodiment, the hydrocarbyl substituent of the acylating agent
has a number average molecular weight of 500 or 750 to 3000, and in
another embodiment 900 to 2000 or 2300.
[0044] In one embodiment, the hydrocarbyl-substituted carboxylic
acid acylating agent for the hydrocarbon lubricant-soluble product
(i) may be made by reacting one or more alpha-beta olefinically
unsaturated carboxylic acid reagents containing 2 to 20 carbon
atoms, exclusive of the carboxyl groups, with one or more olefin
polymers as described more fully hereinafter. The alpha-beta
olefinically unsaturated carboxylic acid reagents may be either
monobasic or polybasic in nature.
[0045] The olefin monomers from which the olefin polymers may be
derived are polymerisable olefin monomers characterized by having
one or more ethylenically unsaturated groups and they (monomers and
polymers).
[0046] In one embodiment, the olefin polymer is a polyisobutene
group (or polyisobutylene group) having a number average molecular
weight of 750 to 3000, and in another embodiment 900 to 2000.
[0047] In one embodiment, the acylating agent for the hydrocarbon
lubricant-soluble product (i) is a hydrocarbyl-substituted succinic
acid or anhydride. The production of these hydrocarbyl-substituted
succinic acids or anhydrides via alkylation of maleic acid or
anhydride or its derivatives with a halohydrocarbon or via reaction
of maleic acid or anhydride with an olefin polymer having a
terminal double bond is well known and need not be discussed in
detail herein.
[0048] In one embodiment, the hydrocarbyl-substituted carboxylic
acid acylating agent for the product hydrocarbon lubricant-soluble
product (i) is a hydrocarbyl-substituted succinic acylating agent
consisting of hydrocarbyl substituent groups and succinic groups.
The hydrocarbyl substituent groups are derived from an olefin
polymer as discussed above. The hydrocarbyl-substituted carboxylic
acid acylating agent is characterized by the presence within its
structure of an average of at least 1.3 succinic groups, and in
another embodiment from 1.5 to 2.5, and in another embodiment form
1.7 to 2.1 succinic groups for each equivalent weight of the
hydrocarbyl substituent. In one embodiment, the
hydrocarbyl-substituted carboxylic acid acylating agent is
characterized by the presence within its structure of 1.0 to 1.3,
and in another embodiment from 1.0 to 1.2, and in another
embodiment from 1.0 to 1.1 succinic groups for each equivalent
weight of the hydrocarbyl substituent.
[0049] In one embodiment, the hydrocarbyl-substituted carboxylic
acid acylating agent is a polyisobutene-substituted succinic
anhydride, the polyisobutene substituent having a number average
molecular weight of 1500 to 3000, and in another embodiment 1800 to
2300, said first polyisobutene-substituted succinic anhydride being
characterized by 1.3 to 2.5, and in another embodiment 1.7 to 2.1
succinic groups per equivalent weight of the polyisobutene
substituent.
[0050] In one embodiment, the hydrocarbyl-substituted carboxylic
acid acylating agent is a polyisobutene-substituted succinic
anhydride, the polyisobutene substituent having a number average
molecular weight of 700 to 1300, and in another embodiment 800 to
1000, said polyisobutene-substituted succinic anhydride being
characterized by 1.0 to 1.3, and in another embodiment 1.0 to 1.2
succinic groups per equivalent weight of the polyisobutene
substituent.
[0051] The hydrocarbon lubricant-soluble product (i) may be formed
using ammonia and/or an amine. The amines useful for reacting with
the acylating agent to form the product (i) include monoamines,
polyamines, and mixtures thereof.
[0052] The hydrocarbon lubricant-soluble product (i) may be a salt,
an ester, an amide, an imide, or a combination thereof. The salt
may be an internal salt involving residues of a molecule of the
acylating agent and the ammonia or amine wherein one of the
carboxyl groups becomes ionically bound to a nitrogen atom within
the same group; or it may be an external salt wherein the ionic
salt group is formed with a nitrogen atom that is not part of the
same molecule. In one embodiment, the amine is a hydroxyamine, the
hydrocarbyl-substituted carboxylic acid acylating agent is a
hydrocarbyl-substituted succinic anhydride, and the resulting
hydrocarbon lubricant-soluble product (i) is a half ester and half
salt, i.e., an ester/salt.
[0053] In one embodiment, the lubricant soluble product (i)
comprises: (i)(a) a first hydrocarbyl-substituted carboxylic acid
acylating agent, the hydrocarbyl substituent of said first
acylating agent having 50 to 500 carbon atoms; and (i)(b) a second
hydrocarbyl-substituted carboxylic acid acylating agent, the
hydrocarbyl substituent of said second acylating agent having 50 to
500 carbon atoms, said first acylating agent and said second
acylating agent being the same or different; said first acylating
agent and said second acylating agent being coupled together by a
linking group derived from a compound having two or more primary
amino groups, two or more secondary amino groups, at least one
primary amino group and at least one secondary amino group, at
least two hydroxyl groups, or at least one primary or secondary
amino group and at least one hydroxyl group; said coupled acylating
agents being reacted with ammonia or an amine. The molecular weight
of the hydrocarbyl substituent for the first acylating agent may be
the same as or it may be different than the molecular weight of the
hydrocarbyl substituent for the second acylating agent.
[0054] In one embodiment, the number average molecular weight for
the hydrocarbyl substituent for the first and/or second acylating
agent is in the range of 1500 to 3000, and in another embodiment
1800 to 2300.
[0055] In one embodiment, the number average molecular weight for
the hydrocarbyl substituent for the first and/or second acylating
agent is in the range of 700 to 1300, and in another embodiment 800
to 1000. The first and/or second hydrocarbyl-substituted carboxylic
acid acylating agent may be a polyisobutene-substituted succinic
anhydride, the polyisobutene substituent having a number average
molecular weight of 1500 to 3000, and in another embodiment 1800 to
2300. This first and/or second polyisobutene-substituted succinic
anhydride may be characterized by at least 1.3, in another
embodiment 1.3 to 2.5, and in another embodiment 1.7 to 2.1
succinic groups per equivalent weight of the polyisobutene
substituent. The first and/or second hydrocarbyl-substituted
carboxylic acid acylating agent may be a polyisobutene-substituted
succinic anhydride, the polyisobutene substituent having a number
average molecular weight of 700 to 1300, and in another embodiment
800 to 1000. This first and/or second polyisobutene-substituted
succinic anhydride may be characterized by 1.0 to 1.3, and in
another embodiment 1.0 to 1.2 succinic groups per equivalent weight
of the polyisobutene substituent. The linking group may be derived
from any of the amines or hydroxamines discussed above having two
or more primary amino groups, two or more secondary amino groups,
at least one primary amino group and at least one secondary amino
group, or at least one primary or secondary amino group and at
least one hydroxyl group. The linking group may also be derived
from a polyol.
[0056] The ratio of reactants utilized in the preparation of these
linked products may be varied over a wide range. Generally, for
each equivalent of each of the first and second acylating agents,
at least one equivalent of the linking compound is used. The upper
limit of linking compound is two equivalents of linking compound
for each equivalent of the first and second acylating agents.
Generally the ratio of equivalents of the first acylating agent to
the second acylating agent is 4:1 to 1:4, and in another embodiment
1.5:1.
[0057] The first and second acylating agents may be reacted with
the linking compound according to conventional ester and/or
amide-forming techniques. This normally involves heating acylating
agents with the linking compound, optionally in the presence of a
normally liquid, substantially inert, organic liquid
solvent/diluent. The reaction between the linked acylating agents
and the ammonia or amine may be carried out under salt, ester/salt,
amide or imide forming conditions using conventional
techniques.
[0058] The ionic or nonionic compound (ii) has a hydrophilic
lipophilic balance (HLB) in the range of 1 to 20 or 30, and in
another embodiment 4 to 15 or 20. Examples of these compounds are
disclosed in McCutcheon's Emulsifiers and Detergents, 1998, North
American & International Edition. Pages 1-235 of the North
American Edition and pages 1-199 of the International Edition are
incorporated herein by reference for their disclosure of such ionic
and nonionic compounds having an HLB in the range of 1 to 10 or 30.
In one embodiment, the ionic or nonionic compound (ii) is a
poly(oxyalkene) compound. These include copolymers of ethylene
oxide and propylene oxide. In one embodiment, the ionic or nonionic
compound (ii) is a hydrocarbon lubricant-soluble product made by
reacting an acylating agent having 12 to 30 carbon atoms with
ammonia or an amine. The acylating agent may contain 12 to 24
carbon atoms, and in another embodiment 12 to 18 carbon atoms. The
amine may be any of the amines described above as being useful in
making the hydrocarbon lubricant-soluble product (i). The product
of the reaction between the acylating agent and the ammonia or
amine may be a salt, an ester, an amide, an imide, or a combination
thereof.
[0059] In one embodiment, the ionic or nonionic compound (ii) is an
ester/salt made by reacting hexadecyl succinic anhydride with
dimethylethanolamine in an equivalent ratio (i.e., carbonyl to
amine ratio) of 1:1 to 1:1.5, and in another embodiment 1:1.35.
[0060] In one embodiment, the ionic or nonionic compound can be the
reaction product of a copolymer of an alpha olefin of 3 to 25
carbon atoms with maleic anhydride reacted with an amine (as
previously described). One such reaction product would be a
copolymer of octadecene with maleic anhydride that is reacted with
triethylenetetramine or dimethylaminopropylamine. It may be
desirable to control crosslinking with these multifunctional
reactants by having large amounts of carboxylic acids of lower
functionality and/or amines of lower functionality present to avoid
forming an insoluble product.
The Second Phase
[0061] The second phase comprises a metal base, an aqueous medium
and optionally a compound containing two or more hydroxyl
groups.
Metal Base
[0062] In several embodiments, the metal base in the form of an
alkali or alkaline earth metal oxide, hydroxide, carbonate,
bicarbonate; or combinations thereof. Examples of the metal base
include calcium oxide, calcium hydroxide, calcium carbonate,
calcium bicarbonate, magnesium oxide, magnesium hydroxide,
magnesium carbonate or magnesium bicarbonate. In one embodiment,
the metal base is a calcium base and in another embodiment a
magnesium base. The metal base may be prepared in a laboratory,
commercially quarried or mixtures thereof.
[0063] In several embodiments, the total surface area of the metal
base as determined by nitrogen BET methods known in the art include
60 m.sup.2g.sup.-1 or less, 50 m.sup.2g.sup.-1 or less or 40
m.sup.2g.sup.-1 or less. Examples of ranges for the total surface
area of the metal base include 0.1 m.sup.2g.sup.-1 to 20
m.sup.2g.sup.-1, 1 m.sup.2g.sup.-1 to 15 m.sup.2g.sup.-1 or 2
m.sup.2g.sup.-1 to 10 m.sup.2g.sup.-1.
[0064] In several embodiments, the metal base mean particle size as
determined after cooling by Coulter.RTM. LS230 Particle Size
Analyser include 0.01 .mu.m to 50 .mu.m, 0.1 .mu.m to 30 .mu.m,
0.15 .mu.m to 20 .mu.m or 0.2 .mu.m to 10 .mu.m.
[0065] In several embodiments, the metal base Zeta Potential
includes 0.1 mV to 100 mV, 1 mV to 75 mV or 2 mV to 20 mV.
[0066] A person skilled in the art will appreciate that the
relationship between zeta potential, mean particle size and total
surface area is a complex relationship. Consequently, a suitable
metal base may have at least one or two of said characteristics
outside the scope of the ranges disclosed above provided that an
emulsion composition formed using said metal base has a
filterability of more than 8 ml/min in the filterability test
disclosed herein.
[0067] In one embodiment, the metal base has combination of at
least two of said characteristics (zeta potential, mean particle
size and total surface area) inside the scope of the ranges
disclosed above. If at least one of said characteristics is outside
the scope of the ranges covered, typically the presence of a
compound containing two or more hydroxyl groups aids filterability
allowing an emulsion composition to have a filterability value of
more than 8 ml/min in the filterability test disclosed herein.
[0068] In one embodiment, the present invention provides an
emulsion composition comprising:
[0069] (a) a first phase comprising: [0070] (i) an oil soluble
inert medium; and [0071] (ii) an emulsifier capable of forming a
water-in-oil emulsion; and
[0072] (b) a second phase comprises: [0073] (i) a metal base;
[0074] (ii) an aqueous medium; and [0075] (iii) optionally a
compound containing two or more hydroxyl groups, wherein the metal
base has combination of at least two of said characteristics (zeta
potential, mean particle size and total surface area) inside the
scope of the ranges disclosed above.
[0076] In one embodiment, the metal base has a nitrogen surface
area below 20 m.sup.2g.sup.-1 and these materials may be employed
over the whole scope of the invention. Examples of a commercially
available metal base include calcium hydroxide (milk of lime)
available from Lhoist with a low nitrogen BET total surface area of
about 2 m.sup.2g.sup.-1, or about 10 m g as described in the patent
application filed by `Lhoist Recherche& Developpement` in
Belgium on 28 Jul. 2003 (filing number 2003/0426) with a PCT filing
date of 27 Jul. 2004 (filing number PCT/EP2004/051609).". Other
commercial suppliers of similar calcium hydroxide materials include
Omya UK Limited or Mississippi Lime Company.
[0077] In one embodiment, the presence of a compound containing two
or more hydroxyl groups further aids filterability of a metal base
having all said characteristics within the ranges of the disclosed
herein.
[0078] In one embodiment, the metal base has a nitrogen surface
area above 20 m.sup.2g.sup.-1 and these materials may be employed
in the presence of a compound containing two or more hydroxyl
groups. Examples of a commercially available metal base include
Wolfrasorp.TM. DSP (nitrogen BET total surface area of about 40
m.sup.2g.sup.-1, commercially available from Lhoist) or
Precal.TM.72 commercially available from Schaefer.
[0079] Alternatively, a suitable calcium hydroxide may be prepared
by the preparative example P-1.
P-1
[0080] 1.5 kg of calcium hydroxide slurry is prepared by blending
22 wt % solid and 78 wt % of de-ionised water in a vessel. The
contents of the vessel are stirred with a paddle stirrer for one
hour. The slurry is then subjected to grinding step to reduce the
particle size of the slurry. The grinding is carried out in a using
a vertical bead mill by placing 300 g of the slurry into a grinding
flask with 700 g of 4 mm glass beads (grinding media) and milling
for 3 hours or until the mean particle size is below 20 .mu.m.
Aqueous Medium
[0081] The aqueous medium includes water or another oil insoluble
solvent or a blend(s) thereof. Water soluble organic materials or
salts may be added to depress the freezing point of the
water/solvent and/or to make the water/solvent more effective in
dissolving or dispersing the base.
[0082] The water used may be taken from any source and includes
tap, deionised, de-ionised to a conductivity of <30
microsiemens/cm; demineralised, purified, recycled water, gray ship
water, seawater or mixtures thereof.
[0083] In one embodiment, the aqueous medium includes an oil
insoluble solvent such as a monohydric alcohol containing 1 to 5
carbon atoms or a polyhydric alcohol containing 2 to 5 carbon
atoms, an ether, and various other solvents that are not soluble in
SAE 30 paraffinic oils to an extent of 1 g/100 ml of oil at
25.degree. C.
[0084] Generally, the aqueous medium and metal base is in the form
of a slurry. As a consequence, the total combined amount of the
aqueous medium and metal base present is in one embodiment at 0.01
wt % to 40 wt %, in another embodiment at 1 wt % to 35 wt %, in
another embodiment at 5 wt % to 30 wt % and in another embodiment
at 10 wt % to 22 wt % of the emulsion composition.
[0085] Generally, the slurry may have a solids content of metal
base in one embodiment of greater than 15 wt %, in another
embodiment above 20 wt %. Examples of a range of the solids content
present include 16 wt % to 40 wt % or 20 wt % to 30 wt %.
Compound Containing Two or More Hydroxyl Groups
[0086] The invention optionally includes a compound containing two
or more hydroxyl groups. In one embodiment, the compound containing
two or more hydroxyl groups is present.
[0087] The compound containing two or more hydroxyl groups is
present in one embodiment from 0 wt % to 10 wt %, in another
embodiment 0.05 wt % to 5 wt %, in another embodiment from 0.05 wt
% to 4 wt % and in another embodiment from 0.1 wt % to 3 wt % of
the emulsion composition.
[0088] The compound containing two or more hydroxyl groups in one
embodiment contains 2 to 12 hydroxyl groups, in another embodiment
2 to 10 hydroxyl groups an in another embodiment 2 to 8 hydroxyl
groups.
[0089] The compound containing two or more hydroxyl groups includes
an ethylene glycol, including di-, tri- and tetraethylene glycol; a
propylene glycol, including di-, tri- and tetrapropylene glycol; a
glycerol; butane diol; hexane diol; sorbitol; arabitol; mannitol;
sucrose; fructose; glucose; cyclohexane diol; erythritol; and
pentaerythritols, including di- and tri- pentaerythritol; or
mixtures thereof. In one embodiment the compound containing two or
more hydroxyl groups is ethylene glycol, diethylene glycol,
triethylene glycol, glycerol, sorbitol, pentaerythritol
dipentaerythritol or mixtures thereof.
Other Performance Additive
[0090] The emulsion composition optionally further includes at
least one other performance additive. The other performance
additive compounds include a metal deactivator, a detergent, a
dispersant, an extreme pressure agent, an antiwear agent, an
antioxidant, a friction modifier, a corrosion inhibitor, a foam
inhibitor, a demulsifiers, a pour point depressant, a seal swelling
agent or mixtures thereof. In one embodiment the emulsion
composition further contains a detergent, a dispersant or mixtures
thereof.
[0091] The total combined amount of the other performance additive
compounds present on an oil free basis in ranges from 0 wt % to 25
wt %, in one embodiment 0.01 wt % to 20 wt %, in another embodiment
0.1 wt % to 15 wt % and in yet another embodiment 0.5 wt % to 10 wt
% of the emulsion composition. Although one or more of the other
performance additives may be present, it is common for the other
performance additives to be present in different amounts relative
to each other.
Dispersants
[0092] Optionally, the invention further comprises a dispersant.
The dispersant is known and includes an ashless-type dispersant.
The ashless type dispersant are characterised by a polar group
attached to a relatively high molecular weight hydrocarbon chain.
Typical ashless dispersants include N-substituted long chain
alkenyl succinimides. Examples of N-substituted long chain alkenyl
succinimides include polyisobutylene succinimide with number
average molecular weight of the polyisobutylene substituent in the
range 350 to 5000, in one embodiment 500 to 3000. Succinimide
dispersants and their preparation are disclosed, for instance in
U.S. Pat. No. 4,234,435. Succinimide dispersants are typically the
imide formed from a polyamine, typically a poly(ethyleneamine).
[0093] In one embodiment, the invention further comprises at least
one dispersant derived from polyisobutylene succinimide with number
average molecular weight in the range 350 to 5000, in one
embodiment 500 to 3000. The polyisobutylene succinimide may be used
alone or in combination with other dispersants.
[0094] In one embodiment, the invention further comprises at least
one dispersant derived from polyisobutylene, an amine and zinc
oxide to form a polyisobutylene succinimide complex with zinc. The
polyisobutylene succinimide complex with zinc may be used alone or
in combination.
[0095] Another class of ashless dispersant is Mannich bases.
Mannich dispersants are the reaction products of alkyl phenols with
aldehydes (especially formaldehyde) and amines (especially
polyalkylene polyamines). The alkyl group typically contains at
least 30 carbon atoms.
[0096] The dispersants may also be post-treated by conventional
methods by a reaction with any of a variety of agents. Among these
are urea, thiourea, dimercaptothiadiazoles, carbon disulfide,
aldehydes, ketones, carboxylic acids, hydrocarbon-substituted
succinic anhydrides, maleic anhydride, nitriles, epoxides, boron
compounds, and phosphorus compounds.
[0097] In one embodiment of the invention, the dispersant is
borated using a variety of agents selected from the group
consisting of the various forms of boric acid (including metaboric
acid, HBO.sub.2, orthoboric acid, H.sub.3BO.sub.3, and tetraboric
acid, H.sub.2B.sub.4O.sub.7), boric oxide, boron trioxide, and
alkyl borates. In one embodiment, the borating agent is boric acid
which may be used alone or in combination with other borating
agents.
[0098] The borated dispersant may be prepared by blending the boron
compound and the N-substituted long chain alkenyl succinimides and
heating them at a suitable temperature, typically 80.degree. C. to
250.degree. C., in one embodiment 90.degree. C. to 230.degree. C.
and in another embodiment 100.degree. C. to 210.degree. C., until
the desired reaction has occurred. The molar ratio of the boron
compounds to the N-substituted long chain alkenyl succinimides is
typically 10:1 to 1:4, in one embodiment 4:1 to 1:3, and in another
embodiment 1:2. An inert liquid may be used in performing the
reaction. The liquid may include toluene, xylene, chlorobenzene,
dimethylformamide and mixtures thereof.
[0099] The dispersant is present in one embodiment from 0 wt % to
10 wt %, in another embodiment 0.01 wt % to 5 wt %, in another
embodiment 0.05 wt % to 3.5 wt % and in another embodiment 0.1 wt %
to 3 wt % of the emulsion composition.
Detergent
[0100] The invention optionally includes a detergent. The detergent
is known and includes neutral or overbased, Newtonian or
non-Newtonian, basic salts of alkali, alkaline earth and transition
metals with one or more hydrocarbyl sulphonic acid, salixarene (the
organic substrate used to prepare a salixarate), carboxylic acid,
phosphorus acid, mono- and/or di-thiophosphoric acid, alkyl phenol,
sulphur coupled alkyl phenol compounds, salixarates, saligenins,
sulphonates, phenates, sulphur-containing phenates or mixtures
thereof. Commonly used metals include sodium, potassium, calcium,
magnesium lithium or mixtures thereof. Most commonly used metals
include sodium, magnesium, calcium or mixtures thereof. Detergents
and in particular overbased detergents and their preparation are
disclosed in U.S. Pat. No. 3,629,109.
[0101] The detergent is present in one embodiment from 0 wt % to 10
wt %, in another embodiment 0.05 wt % to 9 wt %, in another
embodiment from 0.1 wt % to 8 wt %, in another embodiment 0.5 wt %
to 7 wt % and in another embodiment from 1 wt % to 6 wt % of the
emulsion composition.
[0102] Other performance additives such as corrosion inhibitors
including octylamine octanoate, condensation products of dodecenyl
succinic acid or anhydride and a fatty acid such as oleic acid with
a polyamine; metal deactivators including derivatives of
benzotriazoles, 1,2,4-triazoles, benzimidazoles,
2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles; foam
inhibitors including copolymers of ethyl acrylate and
2-ethylhexylacrylate and optionally vinyl acetate; antioxidant
include a diphenylamine, a hindered phenol, a molybdenum
dithiocarbamates or a sulphurised olefin; extreme pressure agents
including amine or metal salts of alkyl and dialkylphosphoric
acids; demulsifiers including trialkyl phosphates, polyethylene
glycols, polyethylene oxides, polypropylene oxides and (ethylene
oxide-propylene oxide) polymers; pour point depressants including
esters of maleic anhydride-styrene, polymethacrylates,
polyacrylates or polyacrylamides; and friction modifiers including
fatty acid derivatives such as amines, esters, epoxides, fatty
imidazolines, condensation products of carboxylic acids and
polyalkylene-polyamines and amine salts of alkylphosphoric acids
may also be used in the composition of the invention.
Process
[0103] The present invention further provides a process for
preparing an emulsion composition comprising:
[0104] (1) mixing a metal base in an aqueous medium to form a
slurry and optionally a compound containing two or more hydroxyl
groups;
[0105] (2) adding an oil soluble inert medium to the slurry of step
(1) to form an emulsion; and
[0106] (3) adding an emulsifier capable of forming a water-in-oil
emulsion,
wherein a base in the form of an alkali metal or an alkaline earth
metal oxide, hydroxide, carbonate, bicarbonate; or combinations
thereof; and wherein the emulsion composition has a flow rate
through a 45 .mu.m filter of more than 8 ml/min in a filterability
test carried out at ambient temperature and 45 kPa applied vacuum;
wherein the filter has diameter of 5 cm and a mesh size of about 45
.mu.m; and wherein the oil soluble inert medium in the filtration
test is an oil of lubricating viscosity of a SAE 50 base oil.
[0107] In one embodiment the invention provides a process for
preparing an emulsion composition comprising:
[0108] (1) mixing a metal base in an aqueous medium to form a
slurry and a compound containing two or more hydroxyl groups;
[0109] (2) adding an oil soluble inert medium to the slurry of step
(1) to form an emulsion; and
[0110] (3) adding an emulsifier capable of forming a water-in-oil
emulsion, wherein a base in the form of an alkali metal or an
alkaline earth metal oxide, hydroxide, carbonate, bicarbonate; or
combinations thereof; and wherein the emulsion composition has a
flow rate through a 45 .mu.m filter of more than 8 ml/min in a
filterability test carried out at ambient temperature and 45 kPa
applied vacuum; wherein the filter has diameter of 5 cm and a mesh
size of about 45 .mu.m; and wherein the oil soluble inert medium in
the filtration test is an oil of lubricating viscosity of a SAE 50
base oil.
[0111] The temperature the process is carried out at for steps (1)
to (3) in one embodiment is 15.degree. C. to 130.degree. C., in
another embodiment 20.degree. C. to 120.degree. C. and in another
embodiment 25.degree. C. to 110.degree. C. The process is carried
out for a period of time in one embodiment for 30 seconds to 48
hours, in another embodiment 2 minutes to 24 hours, and in another
embodiment 5 minutes to 16 hours. The process is carried out at a
pressure in one embodiment of 86.4 kPa to 266 kPa (650 mm Hg to
2000 mm Hg), in another embodiment 91.8 kPa to 200 kPa (690 mm Hg
to 1500 mm Hg), and in another embodiment 95.1 kPa to 133 kPa (715
mm Hg to 1000 mm Hg).
[0112] The process optionally includes mixing other performance
additives as described above. The optional performance additives
may be added sequentially, separately to step (2) and/or step (3).
In one embodiment the process provides the emulsion composition as
a concentrate.
Industrial Application
[0113] The compositions of the present invention are useful as
detergents in an internal combustion engines, for example diesel
fuelled engines, gasoline fuelled engines, natural gas fuelled
engines or a mixed gasoline/alcohol fuelled engines.
[0114] In one embodiment of the invention provides a method for
lubricating an internal combustion engine, comprising supplying
thereto a lubricant comprising the emulsion composition as
described herein. The invention is suitable for an internal
combustion engines such as a 2-stroke or a 4-stroke marine diesel
engine, especially a 2-stroke engine. The use of the emulsion
composition in an internal combustion engine may impart one or more
property from cleanliness, spreadability, corrosive wear resistance
and improved filterability.
[0115] The following examples provide an illustration of the
invention. These examples are non exhaustive and are not intended
to limit the scope of the invention.
EXAMPLES
Examples 1 to 16 and Reference Examples 1 and 2
[0116] An emulsion composition is prepared by blending a milk of
lime with a solids content as shown in Table 1; 1.2 wt % of a
hydrocarbyl substituted carboxylic acid acylating agent emulsifier;
0.01 wt % of an antifoam agent; 0.5 wt % of a dispersant; and 3.8
wt % of a mixture of an overbased and a neutral detergent,
optionally a compound containing 2 or more hydroxyl groups present
at 1 wt % or 2 wt % as shown in Table 1; and the balance of the
emulsion composition is an oil of lubricating viscosity.
TABLE-US-00001 TABLE 1 Milk Hydroxy of Lime Hydroxy Compound Solids
Example Compound (wt %) Milk of Lime Content REF 1 None -- Precal
72 19.1 REF 2 None -- Wolfrasorp DSP 23.8 EX 1 None -- Lhoist low
TSA 18.1 EX 2 Sorbitol 0.43 Lhoist low TSA 18.7 EX 3 Ethylene
Glycol 1 Lhoist low TSA 19 EX 4 Ethylene Glycol 2 Lhoist low TSA 19
EX 5 Glycerol 1 Lhoist low TSA 19 EX 6 Glycerol 2 Lhoist low TSA 19
EX 7 Sorbitol 1 Lhoist low TSA 25 EX 8 Sorbitol 2 Lhoist low TSA 25
EX 9 Sorbitol 0.43 Precal 72 20.3 EX 10 Ethylene Glycol 1 Precal 72
20.3 EX 11 Ethylene Glycol 2 Precal 72 20.3 EX 12 Glycerol 1 Precal
72 20.3 EX 13 Glycerol 2 Precal 72 20.3 EX 14 Sorbitol 0.43
Wolfrasorp DSP 21.5 EX 15 None -- Durcal 5 20.6 EX 16 Sorbitol 0.43
Durcal 5 22.5 EX 17 None -- Lhoist* 23.6 EX 18 Sorbitol 0.43
Lhoist* 22.7 Footnote to Table 1: wt % of sorbitol is based on
using a 70% aqueous solution of sorbitol; Lhoist TSA is Lhoist a
milk of lime with a low nitrogen BET total surface area of about 10
m.sup.2g.sup.-1; and Lhoist* is a milk of lime with a nitrogen BET
total surface area of about 2 m.sup.2g.sup.-1.
Reference Example 3 (REF3) is the same as Reference Example 1,
except the formulation has been stored for 2 weeks.
Test 1: Spreadability
[0117] The spreadability of a sample droplet was measured using a
AMB310H.TM. moisture analyzer available from LabPlant. The
experimental procedure involves placing a sample pan composed of
cast iron on the moisture analyzer balance and then closing the lid
before heating using a halogen lamp to 150.degree. C. or
250.degree. C. and holding until the temperature had equilibrated.
1 drop of sample was then dropped from 1 cm above the sample pan
and droplet was allowed to spread. When the droplet stopped
spreading the area covered was measured. Typically better results
are obtained for samples with a higher spreading area. The results
obtained were:
TABLE-US-00002 TABLE 2 Spreadability surface Spreadability surface
Example area (cm.sup.2) at 150.degree. C. area (cm.sup.2) at
250.degree. C. REF 1 1.65 3.30 EX 2 1.67 2.15 EX 9 1.54 1.44
[0118] The analysis indicates the emulsion composition of the
invention has improved spreadability over the reference example. As
a consequence less corrosive wear is anticipated.
Test 2: Bolnes Engine Test
[0119] The Bolnes Engine Test is a turbocharged, 3 cylinder, 2
stroke, low speed marine diesel engine. The Bolnes engine test
allows the simultaneous testing of three different cylinder oils
over a 72 hour period. Several parameters were rated/measured in
the test. The most important ones are cleanliness ratings, piston
ring wear, cylinder liner wear and analyses of the cylinder drain
samples. The piston ring grooves, lands and skirt and the
scavenging port clogging are rated for cleanliness. The weight loss
of the rings is recorded as a measure of piston ring wear. The
cylinder drain samples are analysed for TBN, and ICP/AES
(Inductively Coupled Plasma Atomic Emission Spectroscopy).
[0120] Examples REF1 and EX1 were run in cylinders 1 and 2
respectively and before passing into the cylinder samples were
passed through a 45 micron sintered ball filter. The results
obtained for REF1 and EX1 were:
TABLE-US-00003 TABLE 3 Engine Run Data Analysed Time (hr) EX1 REF1
Iron Content from 0 0 0 ICP 24 262 899 48 550 1226 72 689 1305
Groove and Liner 72 6.84 7.28 Average Merit Rating Linear Corrosion
72 small area large area of of trace trace to light Linear Scuffing
72 none trace Honing remaining 72 45% 20% on the linear
[0121] The analysis indicates the emulsion composition of the
invention has reduced wear and improved cleanliness compared to the
reference example.
Test 3: Filter Blockage
[0122] The filter blockage was determined by measuring the
percentage of sample filtered and a sample flow rate using a "Total
Sediment in Residual Fuel Oils and Distillate Blends Vacuum Filter
Rig" available from equipment manufacturer SetaClean. The
experimental procedure involved adding approximately 100 ml of the
examples into a calibrated measuring cylinder. The emulsion was
slowly added to the sample cup on the filtration rig and allowed to
sit on the filter membrane for 30 seconds before applying a vacuum
of 45 kPa. The time for the emulsion to filter completely was
recorded and recalculated as a measure of millilitres per minute
and the amount of emulsion filtered was recorded. Typically better
results are obtained for samples with a high filtration flow rates.
The results obtained were:
TABLE-US-00004 TABLE 4 Example Filtration Flow Rate (ml min.sup.-1)
REF 1 0 REF 2 4.6 EX 1 11.07 EX 2 23.62 EX 9 11.13 EX 14 13.45 EX
15 15.71 EX 16 25.75 EX 17 15.75 EX 18 21.03
[0123] The analysis indicates that the emulsion composition of the
invention has good filterability and filtration flow rates compared
to Reference Example 1.
Test 4: Bohlin Rheometer Test
[0124] A Bohlin rheometer sold under the trade name Gemini.TM.
equipped with a plate-plate measuring geometry is used to determine
the rheological properties of the Ca(OH).sub.2 suspensions during
dewatering. The Ca(OH).sub.2 suspensions is loaded in a dewatering
cell, which allows drainage of the suspension by applying a vacuum
to a porous bottom plate. A pressure difference of 60 kPa is used
for all measurements to obtain reproducible dewatering conditions.
The elastic or storage modulus G' of each Ca(OH).sub.2 suspension
is recorded versus time. The upper plate of the measuring geometry
is kept in contact with the sample surface during the entire course
of the measurement. The results presented in Table 5 were based on
an average of three measurements. Generally better results are
obtained for samples with a longer period of time before the
formation of a filter cake.
TABLE-US-00005 TABLE 5 Time of formation of filter cake as measured
by Example rheology/dewatering technique (seconds) REF 1 55 EX 1 65
EX 9 85 EX 2 100
[0125] The results indicate that the metal base of the invention is
less susceptible to formation of a filter cake.
[0126] In summary the emulsion composition has at least one
property from cleanliness, spreadability, corrosive wear resistance
and improved filterability.
[0127] While the invention has been explained, it is to be
understood that various modifications thereof will become apparent
to those skilled in the art upon reading the specification.
Therefore, it is to be understood that the invention disclosed
herein is intended to cover such modifications as fall within the
scope of the appended claims.
[0128] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." Unless otherwise indicated, each
chemical or composition referred to herein should be interpreted as
being a commercial grade material which may contain the isomers,
by-products, derivatives, and other such materials which are
normally understood to be present in the commercial grade. However,
the amount of each chemical component is presented exclusive of any
solvent or diluent oil, which may be customarily present in the
commercial material, unless otherwise indicated. It is to be
understood that the upper and lower amount, range, and ratio limits
set forth herein may be independently combined. Similarly, the
ranges and amounts for each element of the invention may be used
together with ranges or amounts for any of the other elements. As
used herein, the expression "consisting essentially of" permits the
inclusion of substances that do not materially affect the basic and
novel characteristics of the composition under consideration. As
used herein any member of a genus (or list) may be excluded from
the claims.
* * * * *