Note: Descriptions are shown in the official language in which they were submitted.
CA 02273613 1999-06-02
BORATE CONTAINING ADDITIVE FOR
MANUAL TRANSMISSION LUBRICANT BEING STABLE
TO HYDROLYSIS AND PROVIDING HIGH SYNCHROMESH DURABILITY
The present invention relates to extreme pressure (EP) additives for
lubricating oils.
Especially the invention relates to a lubricant additive (preferably
phosphorus free) for
a manual transmission gear box containing potassium triborate having very good
gear
distress prevention properties, high synchromesh durability performance, and
good
water stability performance.
BACKGROUND OF THE INVENTION
High-load conditions often occur in the gear sets used in automotive
transmission
differentials, pneumatic tools; gas compressors, high-pressure hydraulic
systems,
metal-working and similar devices as well as in many types of bearings. In
order to
avoid the undesirable effects which result when using an uncompounded oil
under
these high-load conditions, the lubricants for use in such service contain EP
agents.
For the most part, EP agents have been organic or metallo-organic compounds
which
are oil soluble or are easily incorporated as a stable dispersion in the oil.
Alkali metal borate is well known to the industry for its usefulness as a wear
inhibitor
and extreme pressure agent. In case of a contamination of the lubricant with
water,
additives containing alkali metal borate may not be stable to hydrolysis.
Though alkali
metal borate itself is slightly unstable in presence of water, the other
components of
the package such as friction modifiers, wear inhibitors, and metal
deactivators
deteriorate the hydrolysis stability of the lubricant. It is an object of the
present
invention to provide a lubricant having improved hydrolysis stability, while
preventing
gear distress, protecting the gear against fatigue, and having a high
synchromesh
durability. This last property is of paramount importance for manual
transmission
fluids.
SUMMARY OF THE INVENTION
The present invention provides an extreme pressure additive that improves the
water
stability, oxidation control, high synchromesh durability performance, and
gear
protection of a lubricating oil in a manual transmission gear box. That
additive contains
an alkali-metal borate, an organic polysulfide, an alkyl succinic acid ester
of a polyol,
and an overbased sulfurized alkyl or alkenyl salicylate.
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The alkali-metal borate is present at a level of from 30% to 70%. Preferably,
the
alkali-metal borate is potassium triborate present at a level of from 40% to
66%.
The organic polysulfide is present at a level of from 10% to 30%. Preferably,
the
organic polysulfide is a di-tertiary-butyl-polysulfide present at a level of
from 12% to
25%.
The alkyl succinic acid ester of a polyol is present at a level of from 1% to
20%.
Preferably, the alkyl succinic acid ester is the reaction product of
pentaerythritol
and polyisobutenyl succinic anhydride, and the alkyl succinic acid ester is
present
at a level of from 5% to 15%.
The overbased sulfurized alkyl or alkenyl salicylate is present at a level of
from
0.5% to 20%. Preferably, the overbased sulfurized alkyl or alkenyl salicylate
is
present in an overbased mixture of a sulfurized alkyl salicylate and a
sulfurized
alkyl phenate, and the mixture is present at a level of from 5% to 10%.
Preferably, the extreme pressure additive also has up to 20% of a fatty acid
ester
of a polyol, more preferably a pentaerythritol mono-oleate present at a level
of from
5% to 10%.
In one embodiment, the extreme pressure additive also contains up to 20% of an
alkyl substituted phenyl phosphate, up to 7% of at least one metal
deactivator, and
up to 0.1 % foam inhibitor.
Preferably, the alkyl substituted phenyl phosphate is trixylenyl phosphate
present
at a level of from 5% to 10%.
Preferably, at least one metal deactivator is used, more preferably more than
one
metal deactivator. For example, both 2,5-dimercapto-1,3,4-thiadiazole and
benzotriazole derivative can be used.
The extreme pressure additive can be used in a lubricating oil composition
with a
base oil of lubricating viscosity. That lubricating oil composition can also
contain a
viscosity index improver and a pour point depressant. The high synchromesh
durability performance and gear protection of a manual transmission gear box
can
be improved by adding to the gear box that lubricating oil.
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CA 02273613 2006-12-21
The extreme pressure additive can also be used in a concentrate comprising a
compatible organic liquid diluent and the extreme pressure additive.
According to an aspect of the present invention, there is provided an extreme
pressure additive comprising:
(a) from 30% to 70% of an alkali-metal borate;
(b) from 10% to 30% of an organic polysulfide;
(c) from 1% to 20% of an alkyl succinic acid ester of a polyol; and
(d) from 0.5% to 20% of an overbased sulfurized alkyl or
alkenyl salicylate.
According to another aspect of the present invention, there is provided a
method of
producing an extreme pressure additive comprising blending together:
(a) from 40% to 66% of potassium triborate;
(b) from 12% to 25% of a di-tertiary-butyl-trisulfide;
(c) from 5 to 15% of the reaction product of pentaerythritol and
polyisobutenyl succinic anhydride;
(d) from 5% to 10% of an overbased mixture of a sulfurized alkylsalicylate
and a sulfurized alkylphenate;
(e) from 5% to 10% of pentaerythritol mono-oleate;
(f) from 5% to 10% of trixylenyl phosphate;
(g) from 1% to 3% of 2,5-dimercapto-1,3,4-thiadiazole; and
(h) from 0.5% to 1.5% of a benzotriazole derivative.
DETAILED DESCRIPTION OF THE INVENTION
In its broadest aspect, the present invention involves an extreme pressure
additive
comprising an alkali-metal borate, an organic polysulfide, an alkyl succinic
acid
ester of a polyol, and an overbased sulfurized alkyl or alkenyl salicylate.
Preferably, the additive can further comprise a fatty acid ester of a polyol.
In one
embodiment, the additive can further comprise an alkyl substituted phenyl
phosphate, at least one metal deactivator, and a foam inhibitor.
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CA 02273613 2006-12-21
The high synchromesh durability performance and gear protection of a manual
transmission gear box can be provided by adding to the gear box a lubricating
oil
composition having improved water stability and oxidation control. That
lubricating
oil composition comprises a base oil of lubricating viscosity and the extreme
pressure additive as described above.
Unless otherwise specified, all percentages are in weight percent of the total
additive (calculated without diluent oil) and all ratios are molar ratios.
One method of producing the extreme pressure additive comprises blending
together:
(a) from 40% to 66% of potassium triborate;
(b) from 12% to 25% of di-tertiary-butyl-trisulfide;
(c) from 5% to 15% of the reaction product of pentaerythritol and
polyisobutenyl succinic anhydride;
(d) from 5% to 10% of an overbased mixture of a sulfurized alkylsalicylate
and a sulfurized alkylphenate;
(e) from 5% to 10% of pentaerythritol mono-oleate;
(f) from 5% to 10% of trixylenyl phosphate;
(g) from 1% to 3% of 2,5-dimercapto-1,3,4-thiadiazole;
(h) from 0.5% to 1.5% of benzotriazole derivative; and
(i) up to 0.1 % of a foam inhibitor.
The additive produced by that method might have a slightly different
composition
than the initial mixture, because the components may interact. The components
can be blended in any order and can be blended as combinations of components.
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CA 02273613 1999-06-02
ALKALI-METAL BORATE
In the present invention, the additive contains from 30% to 70% of an alkali-
metal
borate, preferably from 40% to 66% potassium triborate.
The alkali-metal borates are well known in the art and are available
commercially.
Representative patents disclosing suitable borates and methods of manufacture
include U.S. Patent Nos.: 3,313,727; 3,819,521; 3,853,772; 3,907,601;
3,997,454; and
4,089,790. Particularly preferred are the hydrated potassium triborate
microparticies
having a boron-to-potassium molar ratio of about 2.5 to 4.5. At least 90% of
the borate
particles generally have a particle size lower than 0.39 m.
Alkali metal borates are used for the protection of gears against wear
(scoring, pitting,
ridging, rippling), to provide an optimum friction coefficient, and to protect
the
synchronizer ring against wear.
ORGANIC POLYSULFIDE
In the present invention, the additive contains from 10% to 30% of organic
polysulfide,
preferably from 12% to 25% di-tertiary-butyl-trisulfide.
The organic polysulfide is characterized as having sulfide linkages from at
least 2 to
about 10 sulfur atoms, preferably 2 to 6 sulfur atoms, more preferably 2 to 4
sulfur
atoms. The organic polysulfides are generally di, tri, or tetrasulfide
compositions with
trisulfide compositions preferred.
Generally the organic polysulfides contain from 10% to 60% sulfur, preferably
from
20% to 50% sulfur, and more preferably around 44% sulfur.
In its broadest sense, the organic polysulfide molecule may be defined by the
formula:
R,-Sx R2
with x being from 2 to 10. R1 and R2 may be olefinic compounds or alkyl groups
having
from 3 to 30 carbon atoms.
Preferably the organic polysulfide is di-tertiary-butyl-trisulfide which
contains around
44% sulfur.
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Organic polysulfides are introduced in the formulation to provide extreme
pressure
properties to protect gears against distress.
ALKYL SUCCINIC ACID ESTER OF A POLYOL
The alkyl succinic acid ester of a polyol is present at a level of from 1% to
20%.
Preferably, the alkyl succinic acid ester is the reaction product of
pentaerythritol
and polyisobutenyl succinic anhydride, and the alkyl succinic acid ester is
present
at a level of from 5% to 15%.
The process for the preparation of alkenyl or alkyl substituted succinic
anhydrides
involving the reaction of a polyolefin and a maleic anhydride has been
described in
the art. In the case of the classes of compounds described in this invention,
the
alkenyl or alkyl group has a number average molecular weight (Mn) of from 500
to
2500 and a Mw/Mn ratio of from I to 500. The alkenyl or alkyl substituent of
the
succinic anhydride reactant is preferably polymerized isobutene having a Mn of
500 to 1500. Most preferably, it is a polymerized isobutene having a Mn of
from
850 to 1200. The process for producing polyisobutenyl succinic anhydride has
been described in the US Patent No. 3,381,022. The alkyl substituted succinic
anhydride is reacted with polyhydric alcohol such as glycerol,
pentaerythritol, and
sorbitol. Preferably, the aliphatic polyhydric alcohol is pentaerythritol.
This compound is used to improve the stability to hydrolysis and the
compatibility/miscibility of the other parts of the additive.
OVERBASED SULFURIZED ALKYL OR ALKENYL SALICYLATE
The overbased sulfurized alkyl or alkenyl salicylate is present at a level of
from
0.5% to 20%. Preferably it is present in an overbased mixture of a sulfurized
alkylsalicylate and a sulfurized alkylphenate, and the mixture is present at a
level
of from 5% to 10%. Preferably, the salicylate part of that mixture is a single
aromatic ring alkylsalicylate, as is described in the European Patent
Application EP
0 786 448 A2.
The alkylphenols used to prepare the overbased sulfurized alkyl or alkenyl
salicylate contain up to 85% of linear alkylphenol in mixture with at least
15% of
branched alkylphenol in which the branched alkyl radical contains at least
nine
carbon atoms. Preferably, these alkylphenols contain from 35% to 85% of linear
alkylphenol in mixture with from 15% to 65% of branched alkylphenol. The ratio
of
branched versus
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CA 02273613 1999-06-02
linear alkylphenol is given by weight. Preferably, the linear alkyl radical
contains 12 to
40 carbon atoms, more preferably from 18 to 30 carbon atoms, and the branched
alkyl
radical contains at least 9 carbon atoms, preferably from 9 to 24 carbon
atoms, more
preferably 10 to 15 carbon atoms.
This compound is used to improve the stability to hydrolysis and to improve
the
thermal stability and the control of oxidation.
FATTY ACID ESTER OF POLYOL
If used, the fatty acid ester of a polyol is present at a level of up to 20%.
Preferably it is
pentaerythritol mono-oleate present at a level of from 5% to 10%.
The esters useful for this invention are oil-soluble and are preferably
prepared from C8
to C22 fatty acids of the formula R-COOH wherein R is alkyl or alkenyl. The
preferred
esters are obtained from oleic acids: C165118 and C,8-unsaturated.
The ester is synthesized from the previously described fatty acids and polyols
such as
pentaerythritol, glycerol, sorbitol, etc.
This compound is used to have good friction properties, especially to provide
good
conditions for synchronization, and to improve the stability to hydrolysis.
ALKYL SUBSTITUTED PHENYL PHOSPHATE
If used, the alkyl substituted phenyl phosphate is present at a level of up to
20%.
Preferably it is trixylenyl phosphate present at a level of from 5% to 10%.
The phenol
derivative used to obtain this phosphate may be cresol, xylenol, or tri-butyl-
phenol.
This compound is used for its wear inhibition properties, especially for the
protection of
the synchronizer ring.
METAL DEACTIVATOR
If used, the metal deactivator is present at a level of up to 7%. Preferably
it is a
mixture of a 2,5-dimercapto-1,3,4-thiadiazole derivative and a benzotriazole.
The
2,5-dimercapto-1,3,4-thiadiazole derivative is present at a level of up to
3.5%
(preferably from 1% to 3%). The benzotriazole is present at a level of up to
3.5%
(preferably from 0.5 to 1.5%).
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CA 02273613 1999-06-02
The 2,5 dimercapto-1,3,4,-thiadiazole derivative has the following formula
X - G'~ C-X
N"' S~
X may be an R- S or an R - S - S group with R being an alkyl group.
The 2,5 dimercapto-1,3,4,-thiadiazole derivative is used as a metal
deactivator to
prevent copper corrosion and as an extreme pressure agent.
The benzotriazole derivative is a mixture of the N,N-bis (2-ethylhexyl)-4-
methyl-1 H-
benzotriazole-l-methylamine and N,N-bis (2-ethylhexyl)-5-methyl-1 H-
benzotriazole-l-
methylamine. If desired, the benzotriazole derivative can be replaced with a
tolutriazole derivative.
The benzotriazole derivative is used as a metal deactivator to prevent the
corrosion of
copper.
FOAM INHIBITOR
If used, the foam inhibitor is present at a level of up to 0.1 %. Preferably
the foam
inhibitor contains about 3.5% silicon.
LUBRICATING OIL COMPOSITIONS
The additives produced by the process of this invention are useful for
improving the
water stability and oxidation control of lubricating oil compositions. When
employed in
this manner, the amount of the additive ranges from about 0.5% to-40% of the
total
lubricating oil composition, although preferably from about 1 % to 25% of the
total
lubricating oil composition.
The lubricating oil composition comprises a base oil of lubricating viscosity
and the
extreme pressure additive of the present invention. The lubricating oil
composition can
also comprise viscosity index improvers and pour point depressants.
Examples of well-known viscosity index improvers include polymethacrylate type
polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated
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styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity
index
improvers.
An example of a well known pour point depressant is polymethyl methacrylate.
The oil of lubricating viscosity in which the extreme pressure additive is
dispersed
can be any fluid of low dielectric constant which is inert under the reaction
conditions (particularly nonsaponiflable) and of lubricating viscosity. Fluids
of
lubricating viscosity generally have viscosities of from 35 to 50,000 Saybolt
Universal Seconds (SUS) at 100 F (38 C). The fluid medium or oil may be
derived
from either natural or synthetic sources. Included among the natural
hydrocarbonaceous oils are paraffin base, naphthenic base and mixed base oils.
Synthetic oils include polymers of various olefins (generally from 2 to 6
carbon
atoms), alkylated aromatic hydrocarbons, etc. Nonhydrocarbon oils include
polyalkylene oxides such as polyethylene oxide, aromatic ethers, silicone,
etc. The
preferred media are the hydrocarbonaceous oils, both natural and synthetic.
Preferred among the hydrocarbonaceous oils are those having SAE viscosity
numbers of 5W to 20W and 20W to 250W, and especially those having SAE
viscosity numbers in the range 75W to 250W.
The content of the oil of lubricating viscosity in the lubricating oil
composition will
depend on the concentrations of the other components. The lubricating oil
constitutes the balance of the composition after the concentrations of the
borate.
the antiwear agents and the organic sulfur compounds and any other desired
additives have been specified.
ADDITIVE CONCENTRATES
Additive concentrates are also included within the scope of this invention.
The
concentrates of this invention comprise sufficient organic diluent to make
them
easy to handle during shipping and storage.
Suitable organic diluents which can be used include for example, solvent
refined
100N, i.e., Cit-ConTM 100N, and hydrotreated 100N, i.e., RLOP 100N, and the
like.
The organic diluent preferably has a viscosity of from about 1 to about 20 cSt
at
100 C.
Preferably, the organic diluent will constitute less than 10% of the
concentrate.
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CA 02273613 1999-06-02
EXAMPLES
The invention will be further illustrated by following examples, which set
forth
particularly advantageous method embodiments. While the Examples are provided
to
illustrate the present invention, they are not intended to limit it.
HYDROLYSIS STABILITY TEST:
The purpose of the hydrolysis stability tests is to assess the stability of a
fully
formulated lubricant to hydrolysis. Up to 3% water may be introduced by
accident in
the gear box during car wash. The additive has to be stable enough to avoid
chemical
reactions with water. Two tests have been developed to measure the hydrolysis
stability.
For the first test, 3% water is mixed up manually with a fully formulated
lubricant in a
graduated cylinder. The cylinder containing the oil and water is stored at
ambient
temperature for ten days. After ten days, the mixture is visually inspected
looking at
the aspect of the oil, and at the part of the additive which has reacted with
water. This
part has to be 1 ml or lower, and the lubricant has to remain clear, without
haze or gel
formation.
For the second test, 0.5% of water is mixed up with a fully formulated
lubricant with a
mechanical stirring rod in a cylinder. The cylinder is stored at 60 C for one
month.
Then the mixture is visually inspected, looking at the aspect of the oil and
at the
deposit at the bottom of the cylinder. If the bottom of the cylinder is only
covered by
emulsion of oil and water, the result is acceptable. If more than 0.5 ml of
deposit has
been formed on the bottom of the cylinder, reactions between oil and water
have
occurred and the result is no longer acceptable.
EXAMPLE 1
The additive package contained the following compounds:
60.55% potassium tri-borate,
15.14% di-tertiary-butyl-trisulfide containing 44% sulfur,
6.06% the reaction product of a 950 Mw polyisobutene, succinic anhydride and
pentaerythritol,
8.48% overbased sulfurized alkyl salicylate,
6.06% pentaerythritol mono-oleate,
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CA 02273613 1999-06-02
2.42 % 2,5 dimercapto-1,3,4,-thiadiazole derivative,
1.21% benzotriazole derivative which is a mixture of N,N-bis (2-ethylhexyl)-4-
methyl-1 H-benzotriazole-1-methylamine and N,N-bis (2-ethylhexyl)-5-
methyl-1 H-benzotriazole-l-methylamine, and
0.08% silicon-containing foam inhibitor.
The lubricant contained:
8.7% of a concentrate containing 95% of the above additive package and 5%
of a 100N mineral oil,
9.0% polymethacrylate type viscosity index improver,
0.2% polymethacrylate type pour point depressant,
82.1% mixture of 65% of a 90N mineral base oil and 35% of a 600N mineral
base oil.
The SAE grade was 75W-80W, the kinematic viscosity at 100 C was around 7.8
cSt,
and the dynamic viscosity at -440 C was 45000 cP.
The described package demonstrated a good oil and water separation with very
limited reaction with water at ambient temperature (22 C and at 60 C), even
when 3%
of water is added into the package. There was slight deposit at the interface
between
water and oil which was essentially due to water and oil emulsion. This
performance
was evaluated with the previously described in-house procedures.
In the first test (3% of water, oil stored at ambient temperature) the deposit
was less
than 1 ml, the free water was 2 ml, and the aspect of the oil was very clear.
In the second test (0.5% of water, oil stored at 60 C) the bottom was covered
by
oiVwater emulsion and the aspect of the oil was clear.
Protection against gear distress:
The described package provided a very effective protection of gears' teeth
against
adhesive wear and abrasive. This protection against gear distress has been
assessed
through the following tests well known in the industry:
The FZG test rig (CEC L-07-A-95).
This protection remained effective even after oxidation (CEC L-48-A-95
oxidation
procedure at 160 C during 192 hours).
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CA 02273613 2006-12-21
The results were:
= CEC L-07-A-95: pass 12
= CEC L-07-A-95 double speed: pass 12
= CEC L-07-A-95 after oxidation CEC L-48-A-95 160 C 192 hour: damage
load stage = 10.
The API L-37 procedure:
API L-37
Gear tooth surface condition Pinion Ring gear
Burnish Medium-bright Dull
Wear Trace Trace-light
Surface fatigue
= Rippling None None
= Ridging None None
= Pitting None None
= Spalling None None
Scoring None None
Discoloration Light Light-medium
Corrosion None None
Deposits Trace Trace
Pass/Fail assessment Pass 9.95
Surface fatigue protection:
The described package has provided an effective protection of gears' teeth
against surface fatigue (pitting). The protection against pitting was assessed
through the FZG C pitting test run at 90 C. This test is well known in the
industry.
The results of FZG C/8.3/90/1530 were:
first test: 231 hours
second test: 343 hours
third test: 196 hours.
Synchromesh durability:
The described package provided an effective protection of synchronizer's ring
against wear. The synchromesh durability performance of the described
packages was measured with the FZG SSP 180 procedure using AudiTM B80
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CA 02273613 2006-12-21
brass synchronizer. This procedure was run at twice the normal duration. The
protection of Mo/Steel synchronizer, often used in heavy duty trucks, was
evaluated through the ZF synchromesh procedure.
FZG SSP 180 Pass (x2)
(AudiTM B80 Brass >100000
Synchronizer) Axial wear 0.57 - 0.57 mm
HurthTM test rig Axial wear 0.36 - 0.81 mm
Friction coefficient:
Beginning: 0.108/0.11
End:0.099/0.095
FZG SSP 180 Pass
(AudiT"' B80 Brass >200000
Synchronizer) Axial wear: 0.42 - 0.88 mm
HiirthTM test rig Friction coefficient:
(200000 cycles) Beginning: 0.11
100000: 0.095
End: 0.098
ZF synchro test Pass
(Mo/steel synthronizer) >100000
Downshift:
Friction coefficient: 0.079 - 0.085
Axial wear: 0.2 mm
Ring wear: 0.1 mm
Upshift:
Friction coefficient: 0.072 - 0.077
Axial wear: 0.25 mm
Ring wear: 0.1 mm
Oxidation stability:
The described package offered a very efficient protection of mineral lubricant
against oxidation reactions. This fact was assessed through the CEC L-48-A-95
oxidation test run at 160 C during 192 hours, and through the API L-60-1
oxidation test.
Oxidation CEC L-48-A-95 Pass
192 hours at 160 C Viscosity Inc: 1.87 cSt
TAN Inc: 1.4 mg KOH
Deposit: none
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CA 02273613 1999-06-02
API L-60-1
100 C Viscosity increase (%) 55.89
Pentane insoluble (wt. %) 2.8
Toluene insoluble (wt. %) 1.41
Carbon/varnish rating 9.20
Sludge merit rating 9.50
Pass/fail criteria pass
EXAMPLE 2:
The additive package contained the following compounds:
43.92% potassium tri-borate,
28.54% di-tertiary-butyl-trisulfide containing 44% sulfur,
10.98% the reaction product of a 950 Mw polyisobutene, succinic anhydride and
pentaerythritol,
7.69% overbased sulfurized alkyl salicylate,
5.49% pentaerythritol mono-oleate,
3.29% 2,5 dimercapto-1,3,4,-thiadiazole derivative,
0.09% a silicon-containing foam inhibitor.
The lubricant contained:
9.7% of a concentrate containing 94% of the above additive package and 6%
of a 100N mineral oil,
9.0% polymethacrylate type viscosity index improver,
0.2% polymethacrylate type pour point depressant,
81.1% a mixture of 65% of a 90N mineral base oil and.35% of a 600N mineral
base oil.
The SAE grade was 75W-80W, the kinematic viscosity at 100 C was around 7.8
cSt,
and the dynamic viscosity at -40 C is 45000 cP.
The described package demonstrated a good oil and water separation with very
limited reaction with water at ambient temperature (22 C and at 60 C), even
when 3%
of water is added into the package. There was slight deposit at the interface
between
water and oil which was essentially due to water and oil emulsion. This
performance
was evaluated with the previously described in-house procedures.
In the first test (3% of water, oil stored at ambient temperature) the deposit
was 1 ml,
the free water was 2.ml, and the aspect of the oil was clear.
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In the second test (0.5% of water, oil stored at 60 C) the bottom was covered
by
oil/water emulsion and the aspect of the oil was clear.
Protection against gear distress:
The described package provided a very effective protection of gears' teeth
against
adhesive wear and abrasive. This protection against gear distress has been
assessed
through the following tests well known in the industry:
The results of the FZG test rig CEC L-07-A-95: pass 12
Synchromesh durability:
The described package provided an effective protection of synchronizer's ring
against
wear. The synchromesh durability performance of the described packages was
measured with the FZG SSP 180 procedure using Audi B80 brass synchronizer
procedure.
FZG SSP 180 Pass
(Audi B80 brass >100000
synchronizer) Axial wear 0.70 - 0.77 mm
Hurth test rig Friction coefficient:
Beginning:0.107
End: 0.08
Oxidation stability:
The described package offered a very efficient protection of mineral lubricant
against
oxidation reactions. This fact was assessed through the CEC L-48-A-95
oxidation test
run at 160 C during 192 hours, and through the API L-60-1 oxidation test.
Oxidation CEC L-48-A-95 Pass
192 hours at 160 C Viscosity Increase: 3.36 cSt
TAN Increase: 2.7 mg KOH
Deposit: none
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CA 02273613 1999-06-02
EXAMPLE 3:
The additive package contained the following compounds:
65.72% potassium tri-borate,
16.44% di-tertiary-butyl-trisulfide containing 44% sulfur,
6.57% the reaction product of a 950 Mw polyisobutene, succinic anhydride and
pentaerythritol,
9.20% overbased sulfurized alkyl salicylate,
1.31% 2,5 dimercapto-1,3,4,-thiadiazole derivative,
0.66% benzotriazole derivative which is a mixture of N,N-bis (2-ethylhexyl)-4-
methyl-1 H-benzotriazole-1 -methylamine and N,N-bis (2-ethylhexyl)-5-
methyl-1 H-benzotriazole-1-methylamine, and
0.10% silicon-containing foam inhibitor.
The lubricant contained:
8.0% of a concentrate containing 95% of the above additive package and 5%
of a 100N mineral oil,
9.0% polymethacrylate type viscosity index improver,
0.2% polymethacrylate type pour point depressant,
82.8% a mixture of 65% of a 90N mineral base oil and 35% of a 600N mineral
base oil.
The SAE grade was 75W-80W, the kinematic viscosity at 100 C was around 7.8
cSt,
and the dynamic viscosity at -40 C is 45000 cP.
The described package demonstrated a good oil and water separation with very
limited reaction with water at ambient temperature (22 C and at 60 C), even
when 3%
of water is added into the package. There was slight deposit at the interface
between
water and oil which was essentially due to water and oil emulsion. This
performance
was evaluated with the previously described in-house procedures.
In the first test (3% of water, oil stored at ambient temperature) the deposit
was 1 ml,
the free water was 2 ml, and the aspect of the oil was very clear.
In the second test (0.5% of water, oil stored at 60 C) the bottom was covered
by
oiVwater emulsion and the aspect of the oil was clear.
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CA 02273613 1999-06-02
EXAMPLE 4:
The additive package contained the following compounds:
56.45% potassium tri-borate,
22.58% di-tertiary-butyl-trisulfide containing 44% sulfur,
5.65% the reaction product of a 950 Mw polyisobutene, succinic anhydride and
pentaerythritol,
7.90% overbased sulfurized alkyl salicylate,
5.65% pentaerythritol mono-oleate
1.13% 2,5 dimercapto-1,3,4,-thiadiazole derivative,
0.57% benzotriazole derivative which is a mixture of N,N-bis (2-ethylhexyl)-4-
methyl-1 H-benzotriazole-1-methylamine and N,N-bis (2-ethylhexyl)-5-
methyl-1 H-benzotriazole-l-methylamine, and
0.07% silicon-containing foam inhibitor.
The lubricant contained:
9.3% of a concentrate containing 95% of the above additive package and 5%
of a 100N mineral oil,
9.0% polymethacrylate type viscosity index improver,
0.2% polymethacrylate type pour point depressant,
81.5% a mixture of 65% of a 90N mineral base oil and 35% of a 600N mineral
base oil.
The SAE grade was 75W-80W, the kinematic viscosity at 100 C was around 7.8
cSt,
and the dynamic viscosity at ,40 C is 45000 cP.
The described package demonstrated a good oil and water separation with very
limited reaction with water at ambient temperature (22 C and at 609C), even
when 3%
of water is added into the package. There was slight deposit at the interface
between
water and oil which was essentially due to water and oil emulsion. This
performance
was evaluated with the previously described in-house procedures.
In the first test (3% of water, oil stored at ambient temperature) the deposit
was less
than 1 ml, the free water was 2 ml, and the aspect of the oil was clear.
In the second test (0.5% of water, oil stored at 60 C) the bottom was covered
by
oil/water emulsion and the aspect of the oil was clear.
-16-
CA 02273613 1999-06-02
Protection against gear distress:
The described packages provided a very effective protection of gears' teeth
against
adhesive wear and abrasive. This protection against gear distress has been
assessed
through the following test well known in the industry:
The results of the FZG test rig CEC L-07-A-95: pass 12.
Surface fatigue protection:
The described package has provided an effective protection of gears' teeth
against
surface fatigue (pitting). The protection against pitting was assessed through
the FZG
C pitting test run at 90 C. This test is well known in the industry.
The results of FZG C /8.3/90/1530 were:
first test: 266 hours
second test: 343 hours
third test: 175 hours.
Synchromesh durability:
The described package provided an effective protection of synchronizer's ring
against
wear. The synchromesh durability performance of the described packages was
measured with the FZG SSP 180 procedure using Audi B80 brass synchronizer.
This
procedure was run at twice the normal duration. The protection of Mo/Steel
synchronizer, often used in heavy duty trucks, was evaluated through the ZF
synchromesh procedure.
FZG SSP 180 Pass
(Audi B80 brass >100000
synchronizer) Axial wear 0.34 - 0.8 mm
Hurth test rig Friction coefficient:
Beginning:0.102
End: 0.111
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CA 02273613 1999-06-02
ZF synchro test Pass
(Mo/steel synchronizer) >100000
Downshift:
Friction coefficient: 0.082 - 0.085
Axial wear: 0.15 mm
Ring wear: 0.1 mm
Upshift:
Friction coefficient: 0.085 - 0.076
Axial wear: 0.2 mm
Ring wear: 0.15mm
Oxidation stability:
The described package offered a very efficient protection of mineral lubricant
against
oxidation reactions. This fact was assessed through the CEC L-48-A-95
oxidation test
run at 160 C during 192 hours.
Oxidation CEC L-48-A-95 Pass
192 hours at 160 C Viscosity Increase: 2.02 cSt
TAN Increase: 1.87 mg KOH
Deposit: none
EXAMPLE 5:
The additive package contained the following compounds:
60.55% potassium tri-borate,
15.14% di-tertiary-butyl-trisulfide containing 44% sulfur,
6.06% the reaction product of a 950 Mw polyisobutene, succinic anhydride and
pentaerythritol,
8.48% overbased sulfurized alkyl salicylate,
6.06% trixylenyl phosphate
2.42% 2,5 dimercapto-1,3,4,-thiadiazole derivative,
1.21 % benzotriazole derivative which is a mixture of N,N-bis (2-ethylhexyl)-4-
methyl-1 H-benzotriazole-1-methylamine and N,N-bis (2-ethylhexyl)-5-
methyl-1 H-benzotriazole-1 -methylamine, and
0.08% silicon-containing foam inhibitor.
-18-
CA 02273613 1999-06-02
The lubricant contained:
8.7% of a concentrate containing 95% of the above additive package and 5%
of a 100N mineral oil,
9.0% polymethacrylate type viscosity index improver,
0.2% polymethacrylate type pour point depressant,
82.1% a mixture of 65% of a 90N mineral base oil and 35% of a 600N mineral
base oil.
The SAE grade was 75W-80W, the kinematic viscosity at 100 C was around 7.8
cSt,
and the dynamic viscosity at -,40 C is 45000 cP.
The described package demonstrated a good oil and water separation with very
limited reaction with water at ambient temperature (22 C and at 60 C), even
when 3%
of water is added into the package. There was slight deposit at the interface
between
water and oil which was essentially due to water and oil emulsion. This
performance
was evaluated with the previously described in-house procedures.
In the first test (3% of water, oil stored at ambient temperature) the deposit
was less
than 1 ml, the free water was 2 ml, and the aspect of the oil was very clear.
In the second test (0.5% of water, oil stored at 60 C) the bottom was covered
by
oiVwater emulsion and the aspect of the oil was clear.
Protection against gear distress:
The described package provided a very effective protection of gears' teeth
against
adhesive wear and abrasive. This protection against gear distress has been
assessed
through the following test well known in the industry:
The results of the FZG test rig CEC L-07-A-95, double speed: pass 12.
Synchromesh durability:
The described package provided an effective protection of synchronizer's ring
against
wear. The synchromesh durability performance of the described packages was
measured with the FZG SSP 180 procedure using Audi B80 brass synchronizer.
This
procedure was run at twice the normal duration.
-19-
CA 02273613 1999-06-02
FZG SSP 180 Pass (x2)
(Audi B80 brass >100000
synchronizer) Axial wear 0.2 - 0.46 mm
Hurth test rig Axial wear 0.2 - 0.52 mm
Friction coefficient:
Beginning: 0.11/ 0.11
End: 0.100 / 0.106
FZG SSP 180 Pass
(Audi B80 brass >200000
synchronizer) Axial wear: 0.23 - 0.52 mm
Hurth test rig Friction coefficient:
Beginning: 0.11
100000: 0.106
End: 0.101
Oxidation stability:
The described package offered a very efficient protection of mineral lubricant
against
oxidation reactions. This fact was assessed through the CEC L-48-A-95
oxidation test
run at 160 C during 192 hours.
Oxidation CEC L-48-A-95 Pass
192hours at 160 C Viscosity Increase: 1.64 cSt
TAN Increase: 0.9 mg KOH
Deposit: none
EXAMPLE 6:
The additive package contained the following compounds:
59.94% potassium tri-borate,
13.32% di-tertiary-butyl-trisulfide containing 44% sulfur,
13.32% the reaction product of a 950 Mw polyisobutene, succinic anhydride and
pentaerythritol,
6.66% overbased sulfurized alkyl salicylate,
6.66% pentaerythritol mono-oleate, and
0.10% silicon-containing foam inhibitor.
-20-
CA 02273613 1999-06-02
The lubricant contained:
8.0% of a concentrate containing 94% of the above additive package and 6%
of a 100N mineral oil,
5.0% polymethacrylate type viscosity index improver,
0.2% polymethacrylate type pour point depressant,
86.8% a mixture of 65% of a 90N mineral base oil and 35% of a 600N mineral
base oil.
The SAE grade was 75W-80W, the kinematic viscosity at 100 C was around 7.2
cSt,
and the dynamic viscosity at --40 C is 60000 cP.
The described package demonstrated a good oil and water separation with very
limited reaction with water at ambient temperature (22 C and at 60 C), even
when 3%
of water is added into the package. There was slight deposit at the interface
between
water and oil which was essentially due to water and oil emulsion. This
performance
was evaluated with the previously described in-house procedures.
In the first test (3% of water, oil stored at ambient temperature) the deposit
was 1 ml,
the free water was 2 ml, and the aspect of the oil was very clear.
In the second test (0.5% of water, oil stored at 60 C) the bottom was covered
by
oiVwater emulsion and the aspect of the oil was clear.
Protection against gear distress:
The described package provided a very effective protection of gears' teeth
against
adhesive wear and abrasive. This protection against gear distress has been
assessed
through the following test well known in the industry:
35
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CA 02273613 1999-06-02
= API L-37
Gear tooth surface condition Pinion Ring gear
Burnish Medium-bright Dull
Wear Trace Trace
Surface fatigue
= Rippling None None
= Ridging None None
= Pitting None Medium
= Spalling None None
Scoring None None
Discoloration Light Medium
Corrosion None None
Deposits None None
Pass/Fail assessment Pass 9.89
Synchromesh durability:
The described package provided an effective protection of synchronizer's ring
against
wear. The synchromesh durability performance of the described packages was
measured with the ZF synchromesh procedure.
ZF synchro test Pass
(Mo/steel synchronizer) >100000
Downshift:
Friction coefficient: 0.090 - 0.074
Axial wear: 0.25 mm
Ring wear: 0.15mm
Upshift:
Friction coefficient: 0.087 - 0.072
Axial wear: 0.30 mm
Ring wear: 0.15mm
Oxidation stability:
The described package offered a very efficient protection of mineral lubricant
against
oxidation reactions. This fact was assessed through the CEC L-48-A-95
oxidation test
run at 160 C during 192 hours, and through the API L-60-1 oxidation test.
-22-
CA 02273613 1999-06-02
= Oxidation CEC L-48-A-95 Pass
192 hours at 160 C Viscosity Increase: 1.47 cSt
TAN Inc: 1.4 mg KOH
Deposit: none
API L-60-1
100 C Viscosity increase (%) 40.50
Pentane insoluble (wt. %) 2.18
Toluene insoluble (wt. %) 1.60%
Carbon/varnish rating 9.40
Sludge merit rating 9.75
Pass/fail criteria Pass
The previously described examples showed an improvement compared to the
following:
Comparative Example A:
The additive package contained the following compounds:
57.09% potassium tri-borate,
21.40% di-tertiary-butyl-trisulfide containing 44% sulfur,
4.28% primary alcohol zinc dithiophosphate,
7.14% high molecular weight substituted imidazoline,
9.99% low over-based alkyl calcium sulfonate, and
0.10% silicon-containing foam inhibitor.
The lubricant contained:
7.4% of a concentrate containing 95% of the above additive package and 5%
of a 100N mineral oil,
5.0% polymethacrylate type viscosity index improver,
0.2% ol methac late
p y rytype pour point depressant,
87.4% a mixture of 55% of a 90N mineral base oil and 45% of a 600N mineral
base oil.
The SAE grade is 75W-80W, the kinematic viscosity at 100 C is around 7.2 cSt,
and
the dynamic viscosity at -40 C is 60000 cP.
-23-
CA 02273613 1999-06-02
Hydrolytic stability:
The described package has demonstrated a poor oil and water separation with
important reaction with water at ambient temperature 22 C and at 60 C. There
was a
lot of deposit at the interface between water and oil which was essentially
due to the
reaction of some compounds of the additive with water. This performance was
evaluated with the previously described in-house procedures.
In the first test (3% of water, oil stored at ambient temperature) the deposit
was 4 ml,
the free water was 0 ml, and the aspect of the oil was very hazy.
In the second test (0.5% of water, oil stored at 60 C) the deposit was 50 ml.
Protection against gear distress:
The described packages provided a very effective protection of gears' teeth
against
adhesive wear and abrasive. This protection against gear distress has been
assessed
through the following test well known in the industry:
The FZG test rig CEC L-07-A-95: pass 12.
Comparative Example B:
The additive package contained the following compounds:
50.59% potassium tri-borate,
18.97% di-tertiary-butyl-trisulfide containing 44% sulfur,
12.65% the reaction product of a 950 Mw polyisobutene, succinic anhydride and
pentaerythritol,
2.53% primary alcohol zinc dithiophosphate
6.32% high molecular weight substituted imidazoline,
8.85% high over-based alkyl calcium sulfonate, and
0.09% silicon-containing foam inhibitor.
The lubricant contained:
8.3% of a concentrate containing 95% of the above additive package and 5%
of a 100N mineral oil,
5.0% polymethacrylate type viscosity index improver,
0.2% polymethacrylate type pour point depressant,
-24-
CA 02273613 1999-06-02
86.5% a mixture of 55% of a 90N mineral base oil and 45% of a 600N mineral
base oil.
The SAE grade was 75W-80W, the kinematic viscosity at 100 C was around 7.2 cSt
and the dynamic viscosity at -40 C was 60000 cP.
Hydroiytic stability:
The described package had demonstrated a poor oil and water separation with
important reaction with water at ambient temperature 22 C and at 60 C. There
is a lot
of deposit at the inter-face between water and oil which is essentially due to
the
reaction of some compounds of the additive with water. This performance was
evaluated with the previously described in-house procedures.
In the first test (3% of water, oil stored at ambient temperature) the deposit
was 1.5 mi,
the free water was 0 ml, and the aspect of the oil was very hazy.
In the second test (0.5% of water, oil stored at 60 C) the deposit was 8 ml
and the
aspect of the oil was very hazy.
Synchromesh durability:
The described package provided an effective protection of synchronizer's ring
against
wear. The synchromesh durability performance of the described packages was
measured with the FZG SSP 180 procedure using Audi B80 brass synchronizer.
This
procedure was run at twice the normal duration. The protection of Mo/Steel
synchronizer, often used in heavy duty trucks, was evaluated through the ZF
synchromesh procedure.
FZG SSP 180 Pass (x2)
(Audi B80 brass >100000
synchronizer) Axial wear 0.1 - 0.1 mm
Hurth test rig >100000
Axial wear 0.40 - 0.90 mm
-25-
CA 02273613 1999-06-02
ZF synchro test pass
(Mo/steel synchronizer) >100000
Downshift:
Friction coefficient: 0.078 - 0.091
Axial wear: 0.15 mm
Ring wear: 0.1 mm
Upshift:
Friction coefficient: 0.071 - 0.085
Axial wear: 0.2 mm
Ring wear: 0.15mm
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.
25
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