U.S. patent application number 13/988592 was filed with the patent office on 2013-09-19 for functionalized copolymers and lubricating compositions thereof.
This patent application is currently assigned to THE LUBRIZOL CORPORATION. The applicant listed for this patent is Mark R. Baker, William R.S. Barton, Julie Edgar, Michael Huston. Invention is credited to Mark R. Baker, William R.S. Barton, Julie Edgar, Michael Huston.
Application Number | 20130244918 13/988592 |
Document ID | / |
Family ID | 45094801 |
Filed Date | 2013-09-19 |
United States Patent
Application |
20130244918 |
Kind Code |
A1 |
Barton; William R.S. ; et
al. |
September 19, 2013 |
Functionalized Copolymers And Lubricating Compositions Thereof
Abstract
The invention relates to polyester quaternary ammonium salts,
including amine, amide, and ester salts, processes for making them,
and their use as additives, including their use in fuels, such as
diesel fuel and fuel oils. The invention particularly relates to
the use of polyester quaternary ammonium salts as detergents in
fuels and the methods of making them.
Inventors: |
Barton; William R.S.;
(Belper, GB) ; Huston; Michael; (Painesville,
OH) ; Edgar; Julie; (Concord Township, OH) ;
Baker; Mark R.; (Midland, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Barton; William R.S.
Huston; Michael
Edgar; Julie
Baker; Mark R. |
Belper
Painesville
Concord Township
Midland |
OH
OH
MI |
GB
US
US
US |
|
|
Assignee: |
THE LUBRIZOL CORPORATION
Wickliffe
OH
|
Family ID: |
45094801 |
Appl. No.: |
13/988592 |
Filed: |
November 21, 2011 |
PCT Filed: |
November 21, 2011 |
PCT NO: |
PCT/US11/61601 |
371 Date: |
May 21, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61416342 |
Nov 23, 2010 |
|
|
|
Current U.S.
Class: |
508/551 |
Current CPC
Class: |
C10L 1/224 20130101;
C10L 1/265 20130101; C10N 2040/045 20200501; C10M 149/12 20130101;
C10M 149/02 20130101; C10N 2040/046 20200501; C10N 2030/06
20130101; C08G 63/91 20130101; C10L 1/2222 20130101; C10N 2070/00
20130101; C08G 63/912 20130101; C10M 2205/028 20130101; C10L 1/2383
20130101; C10N 2020/071 20200501; C10L 1/238 20130101; C10M 2217/06
20130101; C10N 2040/04 20130101; C10N 2040/042 20200501; C10L 10/18
20130101; C10M 2205/0285 20130101; C10N 2040/30 20130101; C10M
159/123 20130101; C08L 77/12 20130101; C10N 2020/02 20130101; C10L
1/2381 20130101; C10N 2040/08 20130101; C10N 2040/20 20130101; C10N
2030/42 20200501; C10N 2040/044 20200501; C08G 63/6852 20130101;
C10N 2040/25 20130101; C10M 2205/028 20130101; C10M 2209/086
20130101; C10N 2060/09 20200501; C10N 2060/09 20200501; C10M
2205/028 20130101; C10M 2209/086 20130101; C10N 2060/09 20200501;
C10N 2060/09 20200501 |
Class at
Publication: |
508/551 |
International
Class: |
C10M 149/12 20060101
C10M149/12 |
Claims
1. A lubricating composition comprising an oil of lubricating
viscosity and a (thio)phosphate salt of an amine-functionalized
esterified copolymer, wherein the esterified copolymer comprises
units derived from monomers: (i) an .alpha.-olefin and (ii) an
ethylenically unsaturated carboxylic acid or derivative thereof,
esterified with at least one alcohol, and wherein at least a
portion of carboxylic acid groups are reacted with at least one
amine.
2. The lubricating composition of claim 1, wherein the
.alpha.-olefin is a linear or branched olefin, or mixtures
thereof.
3. The lubricating composition of claim 2, wherein the
.alpha.-olefin includes 1-decene, 1-undecene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,
1-heptadecene 1-octadecene, or mixtures thereof.
4. The lubricating composition of claim 3, wherein the
.alpha.-olefin is 1-dodecene.
5. The lubricating composition of claim 1, wherein the
ethylenically unsaturated carboxylic acid or derivative thereof
includes itaconic anhydride, maleic anhydride, methyl maleic
anhydride, ethyl maleic anhydride, dimethyl maleic anhydride or
mixtures thereof.
6. The lubricating composition of claim 1, wherein the
ethylenically unsaturated carboxylic acid or derivative thereof is
maleic anhydride or a derivative thereof.
7. The lubricating composition of claim 1, wherein the
.alpha.-olefin is 1-dodecene and the unsaturated carboxylic acid or
derivative thereof is maleic anhydride.
8. The lubricating composition of claim 1, wherein the copolymer
has, prior to esterification, a reduced specific viscosity of up to
0.08.
9. The lubricating composition of claim 1, wherein the alcohol is a
linear or branched alcohol, a cyclic or acyclic alcohol, or a
combination of features thereof.
10. The lubricating composition of claim 1, wherein the alcohol
comprises a primary alcohol branched at the .beta.- or higher
position and may have at least 12 (or at least 16, or at least 18
or at least 20) carbon atoms.
11. The lubricating composition of claim 1, wherein the alcohol
comprises a mixture of (i) a Guerbet alcohol and (ii) a linear
alcohol containing 6 to 20, or 8 to 18, or 10 to 15 carbon atoms
other than a Guerbet alcohol.
12. The lubricating composition of claim 1, wherein the amine is
capable of providing a TBN (i.e., a total base number) of greater
than 0 mg KOH/g.
13. The lubricating composition of claim 12, wherein the amine
includes an amino-hydrocarbyl morpholine (such as
n-aminopropylmorpholine), an aminoalcohol, vinyl pyridine, N-vinyl
imidazole, a dialkylaminoalkyl (meth)acrylamide or
dialkylaminoalkyl (meth)acrylate, a N-substituted alkanediamine, or
mixtures thereof.
14. The lubricating composition of claim 13, wherein the amino
alcohol includes at least one of dimethylethanolamine,
ethanolamine, isopropanolamine, diethanolamine, triethanolamine,
N,N-diethylethanolamine, N,N-dibutylethanolamine,
3-amino-1,2-propanediol, serinol, 2-amino-2-methyl-1,3-propanediol,
tris(hydroxymethyl)-aminomethane, diisopropanolamine,
N-methyldiethanolamine, 3-(dimethylamino)-2,2-dimethylpropan-1-ol,
and 2-(2-aminoethylamino)ethanol.
15. The lubricating composition of claim 1, wherein the
(thio)phosphate salt is derivable from a (thio)phosphating agent or
(thio)phosphorylating agent which may have phosphorus in its +5
oxidation state.
16. The lubricating composition of claim 15, wherein the
(thio)phosphorylating agent comprises at least one of POCl.sub.3,
P.sub.2O.sub.5, P.sub.4O.sub.10, polyphosphoric acid,
P.sub.2S.sub.5, P.sub.4S.sub.10, phosphoric acid, thiophosphoric
acid, or mixtures thereof.
17. The lubricating composition of claim 15, wherein the
(thio)phosphate salt is a product obtained/obtainable by reacting:
the esterified copolymer with a (thio)phosphate, wherein the
(thio)phosphate is obtained/obtainable by reacting a
hydroxy-containing carboxylic compound (typically a
hydroxy-containing carboxylic acid, or derivatives thereof), a
(typically sulphur-free) phosphating agent, and optionally an
alcohol.
18. A method of lubricating a mechanical device comprising
supplying to the device a lubricating composition of any preceding
claim 1.
19. The method of claim 18, wherein the mechanical device is a
driveline device, such as a manual transmission.
20. The method of claim 18, wherein the mechanical device comprises
at least one of a planetary hub reduction axle, a mechanical
steering and transfer gear box in a utility vehicle, a synchromesh
gear box, a power take-off gear, a limited slip axle, and a
planetary hub reduction gear box.
Description
FIELD OF INVENTION
[0001] The present invention relates to a lubricating composition
comprising an oil of lubricating viscosity and a (thio)phosphate
salt of an amine-functionalized esterified copolymer, wherein the
esterified copolymer comprises units derived from monomers: (i) an
.alpha.-olefin and (ii) an ethylenically unsaturated carboxylic
acid or derivatives thereof, that are esterified with an alcohol,
or mixtures thereof, and wherein at least a portion of carboxylic
acid groups not esterified react with an amine. The invention
further provides for a lubricating composition containing said
copolymer. The invention further provides a method and use of
lubricating composition in a mechanical device.
BACKGROUND OF THE INVENTION
[0002] Viscosity index improvers are known to be added to
lubricating oil compositions to improve the viscosity index of the
lubricant. Typical viscosity index improvers include polymers of
methacrylates, acrylates, olefins (such as copolymers of
alpha-olefins and maleic anhydride and esterified derivatives
thereof), or maleic-anhydride styrene copolymers, and esterified
derivatives thereof. However, such viscosity index improvers can
have poor shear stability, too high a viscosity at low temperature,
poor fuel economy, and poor non-dispersant cleanliness.
[0003] U.S. Pat. Nos. 7,254,249; 4,526,950; 6,419,714; 6,573,224;
6,174,843 6,419,714; and 4,526,950, and International Application
WO 07/133,999 all disclose olefin copolymers for lubricating
compositions
[0004] International publication WO2010/014655 A discloses a
copolymer comprising units derived from monomers (i) an
.alpha.-olefin and (ii) an ethylenically unsaturated carboxylic
acid or derivatives thereof esterified with a primary alcohol
branched at the .beta.- or higher position, wherein the copolymer,
prior to esterification, has a reduced specific viscosity of up to
0.08. The copolymer is useful to provide to a lubricant composition
at least one of acceptable or improved shear stability, acceptable
or improved viscosity index control, acceptable or improved low
temperature viscosity and acceptable or improved oxidation
control.
[0005] Antiwear agents such as phosphate alkyl ammonium chemistry
have been employed in many transmission or axle lubricants as part
of an antiwear package.
[0006] However, many of the amines disclosed may also detrimentally
affect one or more of compatibility with mechanical device seals,
metal corrosion, odour, handling, biodegradability, or oxidative
cleanliness.
[0007] U.S. Pat. No. 3,484,504 discloses the addition reaction
product of oxyalkylenated hydroxy-hydrocarbon phosphate or
thiophosphate and polymeric reaction product containing basic
nitrogen, the latter being (1) the reaction product of an
unsaturated polymerizable ethylenic compound and an unsaturated
polymerizable ethylenic compound containing basic nitrogen or (2)
the reaction product of a polyamine or alkanolamine with the
condensation product of an unsaturated polymerizable ethylenic
compound and polycarboxylic acid, anhydride or ester thereof.
[0008] European Patent Application EP 1495098 A discloses a
lubricating composition comprising a major amount of an oil of
lubricating viscosity and a minor amount of a salt of a phosphorus
acid ester and a nitrogen containing polyacrylate wherein the
phosphorus acid ester is a phosphoric acid ester prepared from
reacting a dithiophosphoric acid with an epoxide or a glycol to
form an intermediate and further reacting the intermediate with a
phosphorus acid or anhydride, wherein the nitrogen containing
polyacrylate is prepared from at least one acrylate or methacrylate
ester and a nitrogen containing monomer, wherein the polyacrylate
is prepared from a combination of: a) methacrylic acid esters
containing from 9 to 25 carbon atoms in the ester group, b)
methacrylic acid esters containing 7 to 12 carbon atoms in the
ester group and at least one nitrogen containing monomer, and
wherein the salt is prepared by combining 0.5 to 10 parts by weight
of the phosphorus acid ester with 99.5 to 90 parts by weight of the
nitrogen containing polyacrylate.
SUMMARY OF THE INVENTION
[0009] An objective of the present invention is to provide an
antiwear additive capable of utilization in a lubricating
composition. Another objective of the present invention is to
provide an additive capable of at least one of the following:
reduced incompatibility with mechanical device seals, decreased
metal corrosion, decreased wear, decreased odour, improved
handling, improved biodegradability, improved oxidative
cleanliness, improved low temperature performance, improved
viscosity index, viscosity modifier performance, or improved
antifoam performance.
[0010] In one embodiment the invention provides a lubricating
composition comprising an oil of lubricating viscosity and a
(thio)phosphate salt of an amine-functionalized esterified
copolymer, wherein the esterified copolymer comprises units derived
from monomers: (i) an .alpha.-olefin and (ii) an ethylenically
unsaturated carboxylic acid or derivative thereof, esterified with
at least one alcohol, and wherein at least a portion of carboxylic
acid groups are reacted with at least one amine.
[0011] As otherwise expressed, the invention provides a lubricating
composition comprising an oil of lubricating viscosity and a
(thio)phosphate salt of an amine-functionalized esterified
copolymer, wherein the esterified copolymer comprises units derived
from monomers (i) an .alpha.-olefin and (ii) an ethylenically
unsaturated carboxylic acid or derivatives thereof (typically
carboxylic acid groups or an anhydride), that are esterified with
an alcohol, or mixtures thereof, and wherein at least a portion of
carboxylic acid groups not esterified react with an amine. Reaction
with the amine may be referred to as capping with an amine. The
amine is typically capable of forming a salt by reaction with a
(thio)phosphate. The copolymer may have a measurable TBN (as
determined by ASTM method D2986).
[0012] The copolymer of the invention may include 400 ppm to 4000
ppm, or 750 ppm to 3000 ppm of phosphorus.
[0013] As used herein the expression "(thio)phosphate" is intended
to include a thiophosphate and a phosphate, and a thiophosphate
also includes a dithiophosphate.
[0014] In one embodiment the invention provides a lubricating
composition comprising an oil of lubricating viscosity and a
(thio)phosphate salt of an amine-functionalized esterified
copolymer, wherein the esterified copolymer comprises units derived
from monomers: (i) an .alpha.-olefin and (ii) an ethylenically
unsaturated carboxylic acid or derivatives thereof, that has been
esterified, with an alcohol, or mixtures thereof, wherein the
alcohol may be a primary alcohol and branched at the .beta.- or
higher position.
[0015] In one embodiment the copolymer may have, prior to
esterification, a reduced specific viscosity of up to 0.08, or 0.02
to 0.08 (or 0.02 to 0.07, 0.03 to 0.07 or 0.04 to 0.06). Typically
the RSV ranges described herein are based on the mean of three
measurements made on the copolymer.
[0016] The copolymer may, instead of RSV, be defined in terms of
weight average molecular weight. Typically the weight average
molecular weight is measured on the final esterified copolymer,
capped with an amine. The weight average molecular weight may be
5000 to 25,000, or 5000 to 20,000, or 10,000 to 18000 or 13,000 to
18,000.
[0017] The copolymer reduced specific viscosity (RSV) is measured
by the formula RSV=(Relative Viscosity-1)/Concentration, wherein
the relative viscosity is determined by measuring, by means of a
dilution viscometer, the viscosity of a solution of 1.6 g of the
copolymer in 100 cm.sup.3 of acetone and the viscosity of acetone
at 30.degree. C. A more detailed description of RSV is provided
below. The RSV is determined for the copolymer of an .alpha.-olefin
and (ii) an ethylenically unsaturated carboxylic acid or
derivatives thereof before esterification.
[0018] In one embodiment the copolymer described above comprises at
least one ester group and a nitrogen containing group (such as
amino-, amido- and/or imido-group), typically sufficient to provide
0.01 wt % to 1.5 wt (or 0.02 wt % to 0.75 wt %, or 0.04 wt % to
0.25 wt %) nitrogen to the copolymer.
[0019] In one embodiment the copolymer may be derived from monomers
(i) an .alpha.-olefin and (ii) an ethylenically unsaturated
carboxylic acid or derivatives thereof,
[0020] wherein 0.1 to 99.89 (or 1 to 50, or 2.5 to 20, or 5 to 15)
percent of the carboxylic acid units esterified are functionalised
with a primary alcohol branched at the .beta.- or higher
position,
[0021] wherein 0.1 to 99.89 (or 1 to 50, or 2.5 to 20, or 5 to 15)
percent of the carboxylic acid units esterified are functionalised
with a linear alcohol or an alpha-branched alcohol,
[0022] wherein 0.01 to 10% (or 0.1% to 20%, or 0.02% to 7.5%, or
0.1 to 5%, or 0.1 to less than 2%) of the carboxylic acid units are
functionalised and have a nitrogen containing group with at least
one of an amino-, amido- and/or imido-group (and may typically
include an aminoalkyl ester, an aminoalkyl amide, or an aminoalkyl
imide). In one embodiment the copolymer has a reduced specific
viscosity of up to 0.08.
[0023] In one embodiment the invention provides a lubricant or
lubricant concentrate obtained (or obtainable) by admixing the
copolymer of the invention with (i) an oil of lubricating
viscosity, and (ii) at least one other performance additives (as
defined below).
[0024] In one embodiment the invention provides a method of
lubricating a mechanical device comprising supplying to the
mechanical device a lubricating composition comprising an oil of
lubricating viscosity and a (thio)phosphate salt of an
amine-functionalized esterified copolymer, wherein the esterified
copolymer comprises units derived from monomers: (i) an
.alpha.-olefin and (ii) an ethylenically unsaturated carboxylic
acid or derivatives thereof, that are esterified with an alcohol,
or mixtures thereof, and wherein at least a portion of carboxylic
acid groups not esterified react with an amine.
[0025] In one embodiment the mechanical device may be a driveline
device.
[0026] In one embodiment the invention provides for the use of the
copolymer disclosed herein to provide to a lubricant composition
with antiwear performance and at least one (or at least two, or
all) of reduced incompatibility with mechanical device seals,
decreased metal corrosion, decreased odour, improved handling,
improved biodegradability, improved oxidative cleanliness, and
improved antifoam performance.
[0027] In one embodiment the invention provides for the use of the
copolymer disclosed herein in an axle oil to provide to a lubricant
composition with antiwear performance and improved antifoam
performance and optionally at least one (or at least two, or all)
of reduced incompatibility with mechanical device seals, decreased
metal corrosion, decreased odour, improved handling, improved
biodegradability, and improved oxidative cleanliness.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The present invention provides a lubricating composition, a
method and use as described above. In one embodiment the invention
also provides a process for the preparation of the copolymer of the
present invention.
[0029] A measurement correlating with molecular weight of the
copolymer (or interpolymer such as an alternating copolymer) may be
expressed in terms of the "reduced specific viscosity" of the
copolymer which is a recognised means of expressing the molecular
size of a polymeric substance. As used herein, the reduced specific
viscosity (abbreviated as RSV) is the value typically obtained in
accordance with the formula RSV=(Relative
Viscosity-1)/Concentration, wherein the relative viscosity is
determined by measuring, by means of a dilution viscometer, the
viscosity of a solution of 1.6 g of the polymer in 100 cm.sup.3 of
acetone and the viscosity of acetone at 30.degree. C. For purpose
of computation by the above formula, the concentration is adjusted
to 1.6 g of the copolymer per 100 cm.sup.3 of acetone. A more
detailed discussion of the reduced specific viscosity, also known
as the specific viscosity, as well as its relationship to the
average molecular weight of a copolymer, appears in Paul J. Flory,
Principles of Polymer Chemistry, (1953 Edition) pages 308 et
seq.
[0030] As used herein, the term "(meth)acryl" and related terms
includes both acrylic and methacrylic groups.
The Copolymer
[0031] The copolymer of the invention prepared by the reaction of
monomers (i) an .alpha.-olefin and (ii) an ethylenically
unsaturated carboxylic acid or derivatives thereof.
[0032] The .alpha.-olefin may be a linear or branched olefin, or
mixtures thereof. If the .alpha.-olefin is linear, the number of
carbon atoms of the .alpha.-olefin may range from 2 to 20, or 4 to
16, or 8 to 12. If the .alpha.-olefin is branched, the number of
carbon atoms of the .alpha.-olefin may range from 4 to 32, or 6 to
20, or 8 to 16. Examples of an .alpha.-olefin include 1-decene,
1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
1-hexadecene, 1-heptadecene 1-octadecene, or mixtures thereof. An
example of a useful .alpha.-olefin is 1-dodecene.
[0033] The ethylenically unsaturated carboxylic acid or derivatives
thereof may be an acid or anhydride or derivatives thereof that may
be partially esterified. When partially esterified, other
functional groups include acids, salts, imides, and amides, or
mixtures thereof. Suitable salts include alkali metal, alkaline
earth metal salts, or mixtures thereof. The salts include lithium,
sodium, potassium, magnesium, calcium salts, or mixtures thereof.
The unsaturated carboxylic acid or derivatives thereof includes
acrylic acid, methyl acrylate, methacrylic acid, maleic acid or
anhydride, fumaric acid, itaconic acid or anhydride or mixtures
thereof, or substituted equivalents thereof.
[0034] Suitable examples of the ethylenically unsaturated
carboxylic acid or derivatives thereof include itaconic anhydride,
maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride,
dimethyl maleic anhydride or mixtures thereof. In one embodiment
the ethylenically unsaturated carboxylic acid or derivatives
thereof includes maleic anhydride, (meth)acrylic acid, or
derivatives thereof such as esters and nitrogen-containing
monomers. Such nitrogen-containing monomers include an
amino-hydrocarbyl morpholine (such as n-aminopropylmorpholine), an
aminoalcohol, N,N-dimethyl acrylamide, a N-vinyl carbonamide (such
as N-vinyl formamide, N-vinyl acetamide, N-vinyl propionamide,
N-vinyl hydroxyacetamide), vinyl pyridine, N-vinyl imidazole,
N-vinyl pyrrolidinone, N-vinyl caproplactam, a dialkylaminoalkyl
(meth)acrylamide or dialkylaminoalkyl (meth)acrylate, a
N-substituted alkanediamaine (such as N-methyl-1,3-propanediamine),
or mixtures thereof.
[0035] The copolymer may be prepared as is described in
International publication WO2010/014655 A. For example, the
copolymer of the invention prepared by the reaction of monomers (i)
an .alpha.-olefin and (ii) an ethylenically unsaturated carboxylic
acid or derivatives thereof are described in paragraph [0140] to
[0141] of WO2010/014655 A. The copolymer may in one embodiment be a
copolymer derived from 1-dodecene and maleic anhydride. Exemplified
copolymers include those prepared below. The esterification and
reaction of the acid monomer with an amine may occur prior to or
after polymerization of the monomers; typically after
polymerization.
[0036] Copolymer Backbone Preparation:
[0037] A copolymer may be prepared by reacting in a 3 litre flask 1
mole of maleic anhydride, and Y moles (defined below) of 1-dodecene
in the presence of 60 wt % of toluene solvent. The flask is fitted
with a flange lid and clip, PTFE stirrer gland, rod and overhead
stirrer, thermocouple, nitrogen inlet port and water-cooled
condenser. Nitrogen is blown through the flask at 0.028 m.sup.3/hr
(or 1 SCFH). A separate 500 ml flask with a side arm is charged
with 0.05 moles of tert-butyl peroxy-2-ethylhexanoate initiator (a
commercially available initiator from Akzo Nobel, known as
Trigonox.RTM.21S), optionally n-dodecyl mercaptan (chain transfer
agent, CTA) and additional toluene. A nitrogen line is fitted to
the arm and nitrogen is applied at 0.085 m.sup.3/hr (or 0.3 SCFH)
for 30 minutes. The 3 litre flask is heated to 105.degree. C. The
Trigonox 21S initiator/toluene mixture is pumped from the 500 ml
flask into the 3 litre flask via a Masterflex.TM. pump (flow rate
set at 0.8 ml/min) over a period of 5 hours. The contents of the 3
litre flask are stirred for 1 hour before cooling to 95.degree. C.
The contents of the 3 litre flask are stirred overnight. Typically
a clear colourless gel is obtained. The amount of each reagent is
shown in the table below.
[0038] The copolymers prepared are characterised by RSV method
described in the description above. The RSV data is presented in
the table.
TABLE-US-00001 Copolymer Prep Y moles of Mole Ratio of CTA Example
1-Dodecene to Initiator RSV Cpp1 1 0:1 0.058 Cpp2 0.95 0:1
0.071
[0039] The copolymer may optionally be prepared in the presence of
a free radical initiator, solvent, chain transfer agent, or
mixtures thereof. A person skilled in the art will appreciate that
altering the amount of initiator and/or chain transfer agent will
alter the number average molecular weight and RSV of the copolymer
of the invention.
[0040] The solvent is known and is normally a liquid organic
diluent. Generally, the solvent has as a boiling point thereof high
enough to provide the required reaction temperature. Illustrative
diluents include toluene, t-butyl benzene, benzene, xylene,
chlorobenzene and various petroleum fractions boiling above
125.degree. C.
[0041] The free radical initiator is known and includes peroxy
compounds, peroxides, hydroperoxides, and azo compounds which
decompose thermally to provide free radicals. Other suitable
examples are described in J. Brandrup and E. Immergut, Editor,
"Polymer Handbook", 2nd edition, John Wiley and Sons, New York
(1975), pages II-1 to II-40. Examples of a free radical initiator
include those derived from a free radical-generating reagent, and
examples include benzoyl peroxide, t-butyl perbenzoate, t-butyl
metachloroperbenzoate, t-butyl peroxide,
sec-butylperoxydicarbonate, azobisisobutyronitrile, t-butyl
peroxide, t-butyl hydroperoxide, t-amyl peroxide, cumyl peroxide,
t-butyl peroctoate, t-butyl-m-chloroperbenzoate,
azobisisovaleronitrile or mixtures thereof. In one embodiment the
free radical generating reagent is t-butyl peroxide, t-butyl
hydroperoxide, t-amyl peroxide, cumyl peroxide, t-butyl peroctoate,
t-butyl-m-chloroperbenzoate, azobisisovaleronitrile or mixtures
thereof. Commercially available free radical initiators include
classes of compound sold under the trademark Trigonox.RTM.-21 from
Akzo Nobel.
[0042] The chain transfer agent is known to a person skilled in the
art. The chain transfer agent may be added to a polymerisation as a
means of controlling the molecular weight of the polymer. The chain
transfer agent may include a sulphur-containing chain transfer
agent such as n- and t-dodecyl mercaptan, 2-mercapto ethanol,
methyl-3-mercaptopropionate. Terpenes can also be used. Typically
the chain transfer agent may be n- and t-dodecyl mercaptan.
[0043] The esterified copolymer may be formed by reaction of
carboxylic acid groups of the ethylenically unsaturated carboxylic
acid or derivatives thereof. The alcohol may be a linear or
branched alcohol, a cyclic or acyclic alcohol, or a combination of
features thereof. The alcohol typically reacts with the
ethylenically unsaturated carboxylic acid or derivatives thereof
(before or after polymerization, typically after) to form
esterified groups.
[0044] The esterified groups may be derivable from linear or
branched alcohols. The alcohol may have 1 to 150, or 4 to 50, or 8
to 20 carbon atoms. Typically the number of carbon atoms is
sufficient to make the copolymer of the invention dispersible or
soluble in oil.
[0045] In different embodiments the alcohol may be a primary
alcohol branched at the .beta.- or higher position may have at
least 12 (or at least 16, or at least 18 or at least 20) carbon
atoms. The number of carbon atoms may range from at least 12 to 60,
or at least 16 to 30.
[0046] The alcohol may be a fatty alcohol of various chain lengths
(typically containing 6 to 20, or 8 to 18, or 10 to 15 carbon
atoms). The fatty alcohol includes Oxo Alcohol.RTM. 7911, Oxo
Alcohol.RTM. 7900 and Oxo Alcohol.RTM. 1100 of Monsanto;
Alphanol.RTM. 79 of ICI; Nafol.RTM. 1620, Alfol.RTM. 610 and
Alfol.RTM. 810 of Condea (now Sasol); Epal.RTM. 610 and Epal.RTM.
810 of Ethyl Corporation; Linevol.RTM. 79, Linevol.RTM. 911 and
Dobanol.RTM. 25 L of Shell AG; Lial.RTM. 125 of Condea Augusta,
Milan; Dehydad.RTM. and Lorol.RTM. of Henkel KGaA (now Cognis) as
well as Linopol.RTM. 7-11 and Acropol.RTM. 91 of Ugine
Kuhlmann.
[0047] The esterified groups may be derivable from Guerbet
alcohols. Guerbet alcohols typically have one or more carbon chains
with branching at the .beta.- or higher position. The Guerbet
alcohols may contain 10 to 60, or 12 to 60, or 16 to 40 carbon
atoms. Methods to prepare Guerbet alcohols are disclosed in U.S.
Pat. No. 4,767,815 (see column 5, line 39 to column 6, line
32).
[0048] The Guerbet alcohols may have alkyl groups including the
following:
[0049] 1) alkyl groups containing C.sub.15-16 polymethylene groups,
such as 2-C.sub.1-15 alkyl-hexadecyl groups (e.g. 2-octylhexadecyl)
and 2-alkyl-octadecyl groups (e.g. 2-ethyloctadecyl,
2-tetradecyl-octadecyl and 2-hexadecyloctadecyl);
[0050] 2) alkyl groups containing C.sub.13-14 polymethylene groups,
such as 1-C.sub.1-15 alkyl-tetradecyl groups (e.g.
2-hexyltetradecyl, 2-decyltetradecyl and 2-undecyltridecyl) and
2-C.sub.1-15 alkyl-hexadecyl groups (e.g. 2-ethyl-hexadecyl and
2-dodecylhexadecyl);
[0051] 3) alkyl groups containing C.sub.10-12polymethylene groups,
such as 2-C.sub.1-15 alkyl-dodecyl groups (e.g. 2-octyldodecyl) and
2-C.sub.1-15 alkyl-dodecyl groups (2-hexyldodecyl and
2-octyldodecyl), 2-C.sub.1-15 alkyl-tetradecyl groups (e.g.
2-hexyltetradecyl and 2-decyltetradecyl);
[0052] 4) alkyl groups containing C.sub.6-9polymethylene groups,
such as 2-C.sub.1-15 alkyl-decyl groups (e.g. 2-octyldecyl) and
2,4-di-C.sub.1-15 alkyl-decyl groups (e.g. 2-ethyl-4-butyl-decyl
group);
[0053] 5) alkyl groups containing C.sub.1-5 polymethylene groups,
such as 2-(3-methylhexyl)-7-methyl-decyl and
2-(1,4,4-trimethylbutyl)-5,7,7-trimethyl-octyl groups; and
[0054] 6) and mixtures of two or more branched alkyl groups, such
as alkyl residues of oxoalcohols corresponding to propylene
oligomers (from hexamer to undecamer), ethylene/propylene (molar
ratio 16:1-1:11) oligomers, iso-butene oligomers (from pentamer to
octamer), C.sub.5-17 .alpha.-olefin oligomers (from dimer to
hexamer).
[0055] Typically the Guerbet alcohol has two alkyl groups with the
difference in the number of carbon atoms between the two alkyl
groups of 4 or less relative to the longer chain alkyl group.
[0056] Examples of suitable primary alcohol branched at the .beta.-
or higher position include 2-ethylhexanol, 2-butyloctanol,
2-hexyldecanol, 2-octyl-dodecanol, 2-decyltetradecanol, or mixtures
thereof.
[0057] In one embodiment the alcohol comprises a mixture of (i) a
Guerbet alcohol and (ii) a linear alcohol other than a Guerbet
alcohol. The other alcohol may be a fatty alcohol described
above.
[0058] The copolymer of the invention may be esterified in the
presence of an alcohol described above. In one embodiment, the
esterified copolymer may be further treated with an alcohol (such
as a C1-C6 alcohol, typically butanol) to react with residual
carboxylic acid groups of the copolymer, thus reducing the acid
number to a desired value. The esterification reaction of the
alcohol with the ethylenically unsaturated carboxylic acid or
derivatives thereof is outlined below.
[0059] Esterified Copolymer:
[0060] The esterified copolymer may be prepared in a flask fitted
with a Dean-Stark trap capped with a condenser. An amount of
copolymer containing 1 mole of carboxy groups is heated in the
flask to 110.degree. C. and stirred for 30 minutes. One mole of
alcohol is added. If the amount of the primary alcohol branched at
the .beta.- or higher position to be charged is greater than one
mole, only one mole is added at this point. Conversely if less than
one mole of the primary alcohol branched at the .beta.- or higher
position is intended, sufficient linear alcohol is used to provide
a total of one mole equivalent of alcohol. The alcohol is pumped
into the flask via peristaltic pump over a period of 35 minutes.
Catalytic amounts of methane sulphonic acid along with the
remaining moles of alcohol are then pumped into the flask over a
period of 5 hours whilst heating to and holding at 145.degree. C.
and removing water in the Dean-Stark trap.
[0061] The reaction temperature is reduced to 135.degree. C., and
sufficient butanol is added sequentially to the flask until the
total acid number (TAN) is not higher than 4 mg KOH/g. The flask is
heated to 150.degree. C. and sufficient sodium hydroxide is added
to quench the methanesulphonic acid. The flask is cooled to ambient
temperature resulting in an esterified copolymer. Optionally, the
product is vacuum stripped to remove any volatile materials such as
water or alcohol.
[0062] The procedure may employ the materials listed in the table
below.
TABLE-US-00002 Moles of Branched Ester Copolymer Moles of Linear
Alcohol Copolymer Prep Alcohol B1 B2 B3 Esc1 Cpp1 2.0 Esc2 Cpp1 1 1
Esc3 Cpp1 1 1 Esc4 Cpp1 1 1 Esc5 Cpp1 1.8 0.2 Esc6 Cpp1 1.8 0.2
Esc7 Cpp1 1.8 0.2 Esc8 Cpp1 0.5 1.5 Esc9 Cpp1 0.5 1.5 Esc10 Cpp1
0.5 1.5 Esc11 Cpp1 2 Esc12 Cpp1 2 Esc13 Cpp1 2 Footnote: The linear
alcohol is a C.sub.8-10 mixture commercially available as Alfol
.RTM.810. Minor amounts of butanol are not included in the reported
amounts. B1 is 2-hexyldecanol. B2 is 2-ethylhexanol. B3 is a
2-octyldodecanol.
Moles of alcohol referred to in the table relate to the total
number of moles of alcohol relative to the total number carboxyl
groups of the unsaturated carboxylic acid of the copolymer.
Typically 2 moles of alcohol react with two moles of carboxyl
groups derived from maleic anhydride.
[0063] The esterified copolymer may be further reacted with an
amine. The amine may include any amine capable of providing, when
incorporated onto the copolymer, a TBN (i.e., a total base number)
of greater than 0 mg KOH/g, or 1 to 20 mg KOH/g, or 2 to 12 mg
KOH/g).
[0064] Examples of the amine include an amino-hydrocarbyl
morpholine (such as n-aminopropylmorpholinc), an aminoalcohol,
N,N-dimethylacrylamide, a N-vinyl carbonamide (such as,
N-vinyl-formamide, N-vinylacetoamide, N-vinyl propionamide, N-vinyl
hydroxyacetoamide, vinyl pyridine, N-vinyl imidazole, N-vinyl
pyrrolidinone, N-vinyl caprolactam, a dialkylaminoalkyl
(meth)acrylamide or dialkylaminoalkyl (meth)acrylate, a
N-substituted alkanediamine (such as d
N-Methyl-1,3-propanediamine), or mixtures thereof.
[0065] Examples of the amine include an amino-hydrocarbyl
morpholine (such as 3-morpholinopropylamine), an amino alcohol, an
N-substituted alkanediamine (such as
N,N-dimethyl-1,3-propanediamine), or mixtures thereof. In one
embodiment the amine may be N,N-dimethyl-1,3-propanediamine
[0066] In one embodiment the amine may be an amino-hydrocarbyl
morpholine (such as 3-morpholinopropylamine), an aminoalcohol or
mixtures thereof.
[0067] The aminoalcohol may include a monoalkanolamine, a
dialkanolamine, a trialkanolamine or mixtures thereof. Examples of
the aminoalcohol include dimethylethanolamine, ethanolamine,
isopropanolamine, diethanolamine, triethanolamine,
N,N-diethylethanolamine, N,N-dimethylethanolamine,
N,N-dibutylethanolamine, 3-amino-1,2-propanediol, serinol,
2-amino-2-methyl-1,3-propanediol, tris(hydroxymethyl)-aminomethane,
diisopropanolamine, N-methyldiethanolamine,
3-(dimethylamino)-2,2-dimethylpropan-1-ol, and
2-(2-aminoethylamino)ethanol.
[0068] When an amine such as an amino-hydrocarbyl morpholine or
another non-hydroxy containing amine is used, the primary amino
group tends to form an imide with the ethylenically unsaturated
carboxylic acid or derivatives thereof. In addition, the phosphate
salt tends to form by subsequent reaction of the acid phosphate
with the tertiary amine. For example the phosphate salt tends to
form by reaction with the tertiary amino group of amino-hydrocarbyl
morpholine, or with the tertiary amino group of N,N-dialkyl
hydrocarbyl (eg N,N-dimethylaminopropylamine reaction
products).
[0069] In one embodiment the amine may be amino-hydrocarbyl
morpholine, an aminoalcohol, or mixtures thereof.
[0070] When an amine such as an aminoalcohol is used, the alcohol
group tends to form (i) an ester with the units derived from the
ethylenically unsaturated carboxylic acid or derivatives thereof if
the amino group is tertiary; and (ii) an ester or amide with the
units derived from the ethylenically unsaturated carboxylic acid or
derivatives thereof if the amino group is primary or secondary. In
addition, the phosphate salt tends to form by subsequent reaction
of the phosphate with the amino group.
[0071] The amine may also include an alkylene polyamine, or
mixtures thereof. The alkylene polyamine may be an ethylene
polyamine, propylene polyamine, butylene polyamine, or mixtures
thereof. Typically the polyamine may be an ethylene polyamine, or
mixtures thereof. Ethylene polyamines, such as some of those
mentioned above, are preferred. They are described in detail under
the heading "Diamines and Higher Amines" in Kirk Othmer's
"Encyclopedia of Chemical Technology", 4th Edition, Vol. 8, pages
74-108, John Wiley and Sons, N.Y. (1993) and in Meinhardt, et al,
U.S. Pat. No. 4,234,435.
[0072] Examples of ethylene polyamine include ethylenediamine,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, N-(2-amino
ethyl)-N'-[2-[(2-aminoethyl)amino]ethyl]-1,2-ethanediamine,
alkylene polyamine still bottoms, or mixtures thereof.
[0073] The alkylene polyamine bottoms may be characterized as
having less than 2%, usually less than 1% (by weight) material
boiling below about 200.degree. C. In the instance of ethylene
polyamine bottoms, which are readily available and found to be
quite useful, the bottoms contain less than about 2% (by weight)
total diethylene triamine (DETA) or triethylene tetramine (TETA). A
typical sample of such ethylene polyamine bottoms obtained from the
Dow Chemical Company of Freeport, Tex., designated "E-100" has a
specific gravity at 15.6.degree. C. of 1.0168, a percent nitrogen
by weight of 33.15 and a viscosity at 40.degree. C. of 121 cSt
(mm.sup.2/s). Gas chromatography analysis of such a sample showed
it contains about 0.93% "Light Ends" (most probably
diethylenetriamine), 0.72% triethylenetetramine, 21.74% tetraethyl
ene pentamine and 76.61% pentaethylene hexamine and higher (by
weight). A similar alkylene polyamine bottoms are commercially sold
under as E100.TM. polyethyleneamines from Dow Chemical.
[0074] The copolymer of the invention may be reacted with an amine
as is shown below.
[0075] Preparative Example of an Esterified Copolymer Capped with
an Amine (Ecca):
[0076] Each esterified copolymer from above is reacted with an
amine in a flask fitted with a Dean-Stark trap capped with a
condenser. Sufficient amine is added to provide the esterified
copolymer with a weight percent nitrogen content as is shown in the
table below. The amine is charged into the flask over a period of
30 minutes and stirred for 2-5 hours at 150.degree. C. The flask is
cooled to 115.degree. C. and drained. The resultant product is
vacuum stripped at 100-150.degree. C. and held for 1.5-2.5 hours.
The procedure employs the materials listed in the table below. The
table below presents the information for a representative number of
esterified copolymers capped with an amine.
TABLE-US-00003 Esterified Nitrogen Content Ecca Copolymer Amine (wt
%) Ecca1 Esc1 Amine 1 0.1 Ecca2 Esc2 Amine 1 0.25 Ecca3 Esc3 Amine
1 0.25 Ecca4 Esc3 Amine 1 0.4 Ecca5 Esc5 Amine 2 0.1 Ecca6 Esc5
Amine 2 0.25 Ecca7 Esc5 Amine 2 0.4 Ecca8 Esc1 Amine 2 0.1 Ecca9
Esc7 Amine 2 0.1 Ecca10 Esc9 Amine 2 0.25 Ecca11 Esc9 Amine 3 0.15
Ecca12 Esc5 Amine 3 0.375 Ecca13 Esc12 Amine 3 0.6 Ecca14 Esc5
Amine 1 0.1 Ecca15 Esc5 Amine 1 0.25 Footnote: Amine 1 is
4-(3-aminopropyl)morpholine Amine 2 is
3-(dimethylamino)-1-propylamine Amine 3 is 1-(3-aminopropyl)
imidazole
[0077] The phosphate salt may be derivable from reacting an
amine-functionalized esterified copolymer, wherein the esterified
copolymer comprises units derived from monomers: (i) an
.alpha.-olefin and (ii) an ethylenically unsaturated carboxylic
acid or derivatives thereof, that are esterified with an alcohol,
or mixtures thereof, and wherein at least a portion of carboxylic
acid groups not esterified react with an amine (typically having
TBN of greater than 0 mg KOH/g, or 1 to 20 mg KOH/g, or 2 to 12 mg
KOH/g) with a (thio)phosphorylating agent.
[0078] In one embodiment the copolymer of the invention comprises
(i) the .alpha.-olefin and (ii) an ethylenically unsaturated
carboxylic acid or derivatives thereof (typically maleic
anhydride), and (iii) one or more additional co-monomers that are
known to copolymerize with the preceding monomers. Suitable
co-monomers include vinyl aromatic monomers; alkyl meth(acrylates);
vinyl acetate; and fumaric acid and derivatives thereof. The vinyl
aromatic monomers include styrene or alkylstyrene (such as
alpha-methylstyrene, para-tert-butylstyrene, alpha-ethylstyrene,
and para-lower alkoxy styrene), or mixtures thereof. In one
embodiment the vinyl aromatic monomer may be styrene.
(Thio)Phosphating Agent
[0079] As used herein, the expression "(thio)phosphorylating agent"
is meant to include a phosphorylating agent, a thiophosphorylating
agent, or mixtures thereof. In one embodiment the phosphorylating
agent does not contain sulphur. As used herein the expression
"(thio)phosphorylating agent" may be used interchangeably with the
expression "(thio)phosphating agent".
[0080] The (thio)phosphorylating agent which may be employed is
typically phosphorus pentoxide, phosphorus pentasulphide, or
reactive equivalents thereof. Reactive equivalents of
thiophosphoric acid or phosphoric acid include acid halides,
esters, amides, anhydrides, salts, partial salts, or mixtures
thereof. The (thio)phosphorylating agent may have phosphorus in its
+5 oxidation state.
[0081] Phosphorus pentoxide is usually referred to as
P.sub.2O.sub.5, which is its empirical formula, and phosphorus
pentasulphide is usually referred to as P.sub.2S.sub.5, which is
its empirical formula, even though it is believed that both
molecules consist at least in part of more complex molecules such
as P.sub.4O.sub.10, or P.sub.4S.sub.10. The (thio)phosphorylating
agent may include POCl.sub.3, P.sub.2O.sub.5, P.sub.4O.sub.10,
polyphosphoric acid, P.sub.2S.sub.5, or P.sub.4S.sub.10, or
mixtures thereof. In one embodiment the (thio)phosphorylating agent
may be a sulphur-free phosphating agent, typically POCl.sub.3,
P.sub.2O.sub.5, P.sub.4O.sub.10, or polyphosphoric acid.
[0082] The (thio)phosphate salt of the amine-functionalized
copolymer, may also be a product obtained/obtainable by reacting:
(i) a hydroxy-containing carboxylic compound (such as a
hydroxy-containing carboxylic acid), or derivatives thereof (the
derivative may include ester, amide, or partial salts of amide or
ester, (typically partial ester), or a compound may be derived from
a partially esterified polyol (such as glycerol)) and/or an alcohol
(typically a monohydric alcohol, or a dihydric alcohol), a
(thio)phosphorylating agent, and esterified ester copolymer capped
with an amine. The resultant product may be referred to as an acid
(thio)phosphate.
[0083] As used herein the expression "acid (thio)phosphate" is
known to a person skilled in the art to include an acid
thiophosphate or an acid phosphate (free of sulphur).
[0084] The acid (thio)phosphate which may be a product
obtained/obtainable by reacting: a hydroxy-containing carboxylic
compound, and/or an alcohol (typically a monohydric alcohol or a
dihydric alcohol), a (thio)phosphorylating agent, and capped with
amine having a basic nitrogen. The amine having a basic nitrogen
when incorporated into the product may have a total base number
(TBN) of greater than 0 mg KOH/g, or 1 to 20 mg KOH/g, or 2 to 12
mg KOH/g.
[0085] In one embodiment the (thio)phosphate salt may be an acid
(thio)phosphate which may be a product obtained/obtainable by
reacting: (i) a hydroxy-containing carboxylic acid, or derivatives
thereof and a (thio)phosphorylating agent, and capped with amine
having a basic nitrogen.
[0086] In one embodiment the (thio)phosphate salt may be an acid
(thio)phosphate which may be a product obtained/obtainable by
reacting: (i) an alcohol (typically a monohydric alcohol or a
dihydric alcohol) and a (thio)phosphorylating agent, and capped
with amine having a basic nitrogen.
[0087] The (thio)phosphorylating agent may be mixed with and
reacted with the hydroxy-containing carboxylic compound, and or
alcohol in any order.
[0088] The (thio)phosphorylating agent itself may also be
introduced into the reaction mixture in a single portion, or it may
be introduced in multiple portions. Thus, in one embodiment an acid
(thio)phosphate product (or intermediate) is prepared wherein a
portion of the (thio)phosphorylating agent is reacted the
hydroxy-containing carboxylic compound, and/or the alcohol and
thereafter a second charge of the (thio)phosphating agent is
added.
[0089] In one embodiment the (thio)phosphate salt of an
amine-functionalized copolymer may be obtained/obtainable by
reacting the product of (i) with esterified ester copolymer capped
with amine having basic nitrogen. The product may be a polymer
bound alkylammonium salt of a (thio)phosphate ester of the
hydroxy-containing carboxylic compound, typically a (thio)phosphate
ester derivative. For example the product may be an alkyl
hydroxy-carboxylate (thio)phosphate polymer bound trialkyl ammonium
salt, or mixtures thereof. The trialkyl ammonium salt may be
derived from an amine having a tertiary amino group as described
below.
[0090] In one embodiment the present invention provides a
lubricating composition comprising an oil of lubricating viscosity
and a (thio)phosphate salt of an amine-functionalized copolymer
obtained/obtainable by reacting: (i) an alcohol (typically a
monohydric alcohol or a dihydric alcohol), or derivatives thereof,
a (thio)phosphorylating agent, and in the absence of a
hydroxy-containing carboxylic compound (typically a
hydroxy-containing carboxylic acid), and optionally (ii) reacting
the product of (i) with an esterified ester copolymer capped with
an amine having a basic nitrogen.
[0091] In one embodiment the present invention provides a
lubricating composition comprising an oil of lubricating viscosity
and a (thio)phosphate salt of an amine-functionalized copolymer
obtained/obtainable by reacting: (i) a hydroxy-containing
carboxylic compound (typically a hydroxy-containing carboxylic
acid, or derivatives thereof), a (thio)phosphorylating agent, and
an alcohol (typically a monohydric alcohol, or a dihydric alcohol),
and optionally (ii) reacting the product of (i) with an amine, or
mixtures thereof. In one embodiment the invention provides a
lubricating composition, wherein the product of (i) is further
reacted with an amine, or mixtures thereof.
[0092] In one embodiment the present invention provides a
lubricating composition comprising an oil of lubricating viscosity
and a (thio)phosphate salt of an amine-functionalized esterified
copolymer, wherein the esterified copolymer comprises units derived
from monomers: (i) an .alpha.-olefin and (ii) an ethylenically
unsaturated carboxylic acid or derivatives thereof (typically
carboxylic acid groups or an anhydride), that are esterified with
an alcohol, or mixtures thereof, and wherein at least a portion of
carboxylic acid groups not esterified react with an amine, wherein
the (thio)phosphate salt is obtained/obtainable by reacting: a
hydroxy-containing carboxylic compound (typically a
hydroxy-containing carboxylic acid, or derivatives thereof), a
(typically sulphur-free) phosphating agent, and optionally an
alcohol.
[0093] The resultant product may then be reacted with the amine of
the esterified copolymer described herein.
[0094] In one embodiment the hydroxy-containing carboxylic compound
may be a hydroxy-carboxylic acid, or derivatives thereof, a
partially esterified polyol, or mixtures thereof.
[0095] The hydroxy-containing carboxylic compound may include a
compound derived from a hydroxy-containing carboxylic acid
represented by the formulae:
##STR00001##
wherein n and m may be independently integers of 1 to 5; X may be
an aliphatic or alicyclic group, or an aliphatic or alicyclic group
containing an oxygen atom in the carbon chain, or a substituted
group of the foregoing types, said group containing up to 6 carbon
atoms and having n+m available points of attachment; each Y may be
independently --O--, >NH, or >NR.sup.1 or two Ys together
representing the nitrogen of an imide structure R--N< formed
between two carbonyl groups; and each R and R.sup.1 may be
independently hydrogen or a hydrocarbyl group, provided that at
least one R or R.sup.1 group is a hydrocarbyl group; each R.sup.2
may be independently hydrogen, a hydrocarbyl group or an acyl
group, further provided that at least one --OR.sup.2 group is
located on a carbon atom within X that is .alpha. or .beta. to at
least one of the --C(O)--Y--R groups, with the proviso that at
least one R.sup.2 group is hydrogen.
[0096] The compound derived from the hydroxy-carboxylic compound
may be derived from glycolic acid (n and m both equal 1), malic
acid (n=2, m=1), tartaric acid (n and m both equal 2), citric acid
(n=3, m=1), or mixtures thereof. In one embodiment the compound
derived from the hydroxy-carboxylic compound may be derived from
tartaric acid or glycolic acid, typically tartaric acid.
[0097] The compound (II) derived from the hydroxy-containing
carboxylic acid may be derived from a partially esterified polyol
(such as glycerol), or mixtures thereof. The partially esterified
polyol may be glycerol monooleate, or glycerol dioleate.
[0098] The alcohol is reacted with the (thio)phosphating agent. The
alcohol includes the monohydric alcohol, or the dihydric alcohol.
The carbon atoms of the alcohol may be in linear chains, branched
chains, or mixtures thereof. When branched, the alcohol may be a
Guerbet alcohol, or mixtures thereof. A branched alcohol may
contain 6 to 40 or 6 to 30, or 8 to 20 carbon atoms (typically 8 to
20 carbon atoms).
[0099] The Guerbet alcohols have been described previously.
[0100] Examples of a suitable branched alcohol include
2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol,
2-decyltetradecanol, iso-tridecanol, iso-octyl, Guerbet alcohols,
or mixtures thereof.
[0101] Examples of a monohydric alcohol include methanol, ethanol,
propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol,
decanol, undecanol, dodecanol, tridecanol, tetradecanol,
pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol,
eicosanol, or mixtures thereof. In one embodiment the monohydric
alcohol contains 6 to 30, or 8 to 20, or 8 to 15 carbon atoms
(typically 8 to 15 carbon atoms).
[0102] The alcohol may include commercially available materials
such as Oxo Alcohol.RTM. 7911, Oxo Alcohol.RTM. 7900 and Oxo
Alcohol.RTM. 1100 of Monsanto; Alphanol.RTM. 79 of ICI; Nafol.RTM.
1620, Alfol.RTM. 610 and Alfol.RTM. 810 of Condea (now Sasol);
Epal.RTM. 610 and Epal.RTM. 810 of Ethyl Corporation (now Afton);
Linevol.RTM. 79, Linevol.RTM. 911 and Dobanol.RTM. 25 L of Shell
AG; Lial.RTM. 125 of Condea Augusta, Milan; Dehydad.RTM. and
Lorol.RTM. of Henkel KGaA (now Cognis) as well as Linopol.RTM. 7-11
and Acropol.RTM. 91 of Ugine Kuhlmann.
[0103] The dihydric alcohol may include an alkylene diol, or
mixtures thereof. The alkane diol may be in a 1,2- or 1,3- or
1,4-arrangement. For example alkane diol hydroxyl groups may be
attached to adjacent carbon atoms (i.e., 1,2- or a vicinal
diol).
[0104] Examples of the alkylene diol include ethylene glycol,
1,2-propylene glycol, 1,2-butylene glycol; also 1,3-propylene diol,
1,3-butylene diol, 1,4-butylene diol, 1,2-hexylene diol,
1,2-dodecylene diol, and 1,2-octadecylene diol.
[0105] In one embodiment the hydroxy-containing carboxylic acid
and/or the alcohol, or derivatives thereof, the
(thio)phosphorylating agent may be reacted at a temperature in the
range of 30.degree. C. to 100.degree. C., or 50.degree. C. to
90.degree. C. The reaction may form a mono- or di-phosphate
ester.
[0106] The reaction of the esterified copolymer and an amine in
step (ii) may be carried out at a temperature in the range of
30.degree. C. to 120.degree. C., or 40.degree. C. to 90.degree.
C.
[0107] In one embodiment the hydroxy-containing carboxylic acid
and/or the alcohol, or derivatives thereof, the
(thio)phosphorylating agent may be reacted at a temperature in the
range of 30.degree. C. to 100.degree. C., or 50.degree. C. to
90.degree. C. in the presence of the esterified copolymer amine.
The reaction may form a mono- or di-phosphate ester.
[0108] The relative amounts of the hydroxy-containing carboxylic
acid, or derivatives thereof to the alcohol may be 1:0 to 0:1, or
0.8:0.2 to 0.2:0.8. At a 1:1 mole ratio of the hydroxy-containing
carboxylic acid, or derivatives thereof having 2 or more hydroxyl
groups to the alcohol (typically a monohydric alcohol, or a
dihydric alcohol), the mole ratio of hydroxyl groups will be
>1:1.
[0109] The hydroxy-containing carboxylic acid, or derivatives
thereof (and optionally the monohydric alcohol or dihydric alcohol)
are reacted with the (thio)phosphorylating agent in such overall
amounts that the product mixture formed thereby contains
(thio)phosphorus acid functionality. That is, the
(thio)phosphorylating agent is not completely converted to its
ester form but will retain at least a portion of P--OH, or P--SH
acidic functionality, which is accomplished by using a sufficient
amount of the (thio)phosphorylating agent compared with the
equivalent amounts of the hydroxy-containing carboxylic acid, or
derivatives thereof (and optionally the alcohol). In particular, in
certain embodiments the (thio)phosphorylating agent (which may
comprise phosphorus pentoxide), may be reacted with the
hydroxy-containing carboxylic acid, or derivatives thereof (and
optionally the alcohol) in a ratio of 1:2.5 moles (or 1.25:2 moles)
of hydroxyl groups per 1 mole of phosphorus from the
(thio)phosphorylating agent.
[0110] In one somewhat oversimplified schematic representation
using P.sub.2O.sub.5 for illustrative purposes, the reaction of the
phosphating agent with alcohol(s) may be represented as
follows:
3ROH+P.sub.2O.sub.5.fwdarw.(RO).sub.2P(.dbd.O)OH+RO--P(.dbd.O)(OH).sub.2
where ROH represent hydroxyl groups of either (i) a
hydroxy-containing carboxylic compound, or derivatives thereof,
(ii) a monoalcohol, (iii) a mixture of a monool and diol, or (iv) a
mixture of the hydroxy-containing carboxylic acid, or derivatives
thereof with an alcohol (typically a monohydric alcohol, or a
dihydric alcohol). As will be seen below, the residual phosphoric
acidic functionality may be reacted at least in part with an
amine.
[0111] The amine may be reacted with the copolymer described above.
The incorporated amine having basic nitrogen may contain a
secondary or tertiary amino group (typically a tertiary amino
group). The incorporated amine may for instance include
dimethylaminopropylamine, N,N-dimethyl-aminopropylamine,
N,N-diethyl-aminopropylamine, N,N-dimethyl-aminoethylamine,
ethylenediamine, 1,2-propylenediamine, 1,3-propylene diamine, the
isomeric butylenediamines, pentanediamines, hexanediamines,
heptanediamines, diethylenetriamine, dipropylenetriamine,
dibutylenetriamine, triethylenetetraamine, tetraethylenepentaamine,
pentaethylenehexaamine, hexamethyleneheptaamine, and
bis(hexamethylene)triamine, 3,3-diamino-N-methyldipropylamine, or
3'3-aminobis(N,N-dimethylpropylamine) or mixtures thereof.
[0112] The amine having basic nitrogen may in one embodiment be
dimethylaminopropylamine, N,N-dimethyl-aminopropylamine,
N,N-diethyl-aminopropylamine, N,N-dimethyl-aminoethylamine
ethylenediamine, 1,2-propylenediamine, or mixtures thereof.
[0113] The amine having basic nitrogen may be substituted
heterocyclic compounds such as 1-(3-aminopropyl)imidazole,
4-(3-aminopropyl)morpholine, 1-(2-amino ethyl)piperidine,
1-(3-aminopropyl)-2-pipecoline, 1-methyl-(4-methylamino)piperidine,
4-(1-pyrrolidinyl)piperidine, 1-(2-aminoethyl)-pyrrolidine,
2-(2-aminoethyl)-1-methylpyrrolidine, or mixtures thereof.
[0114] The amine having basic nitrogen may optionally include
oxygen. The amine of this type may include an alkanolamine such as
N,N-dimethylaminopropanol, N,N-diethylaminopropanol,
N,N-diethylaminobutanol, or mixtures thereof.
[0115] The amine having basic nitrogen may also include amines
having (a tertiary amino group. Amines of this type include
N,N-diethylethylenediamine, N,N-dimethylethylenediamine,
N,N-dibutylethylenediamine, N,N-diethyl-1,3-diaminopropane,
N,N-dimethyl-1,3-diaminopropane, N,N,N'-trimethylethylenediamine,
N,N-dimethyl-N'-ethylethylenediamine,
N,N-diethyl-N'-methylethylenediamine,
N,N,N'-triethylethylenediamine, 3-dimethylaminopropylamine,
3-diethylaminopropylamine, 3-dibutylaminopropylamine,
N,N,N'-trimethyl-1,3-propanediamine,N,N,2,2-tetramethyl-1,3-propanediamin-
e, 2-amino-5-diethylaminopentane,
N,N,N',N'-tetraethyldiethylenetriamine,
3,3'-diamino-N-methyldipropylamine,
3,3'-iminobis(N,N-dimethylpropylamine), or mixtures thereof. In one
particular embodiment the amine having basic nitrogen may be
N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane,
N,N-dimethylethylenediamine, N,N-diethylethylenediamine,
N,N-dibutylethylenediamine, or mixtures thereof.
Oils of Lubricating Viscosity
[0116] The lubricating composition comprises an oil of lubricating
viscosity. Such oils include natural and synthetic oils, oil
derived from hydrocracking, hydrogenation, and hydrofinishing,
unrefined, refined, re-refined oils or mixtures thereof. A more
detailed description of unrefined, refined and re-refined oils is
provided in International Publication WO2008/147704, paragraphs
[0054] to [0056] (a similar disclosure is provided in US Patent
Application 2010/197536, see [0072] to [0073]). A more detailed
description of natural and synthetic lubricating oils is described
in paragraphs [0058] to [0059] respectively of WO2008/147704 (a
similar disclosure is provided in US Patent Application
2010/197536, see [0075] to [0076]). Synthetic oils may also be
produced by Fischer-Tropsch reactions and typically may be
hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one
embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid
synthetic procedure as well as other gas-to-liquid oils.
[0117] Oils of lubricating viscosity may also be defined as
specified in April 2008 version of "Appendix E--API Base Oil
Interchangeability Guidelines for Passenger Car Motor Oils and
Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock
Categories". The API Guidelines are also summarised in U.S. Pat.
No. 7,285,516 (see column 11, line 64 to column 12, line 10). In
one embodiment the oil of lubricating viscosity may be an API Group
II, Group III, Group IV oil, or mixtures thereof.
[0118] The amount of the oil of lubricating viscosity present is
typically the balance remaining after subtracting from 100 wt % the
sum of the amount of the copolymer of the invention and the other
performance additives.
[0119] The lubricating composition may be in the form of a
concentrate and/or a fully formulated lubricant. If the copolymer
of the present invention is in the form of a concentrate (which may
be combined with additional oil to form, in whole or in part, a
finished lubricant), the ratio of the of components the copolymer
of the present invention to the oil of lubricating viscosity and/or
to diluent oil include the ranges of 1:99 to 99:1 by weight, or
80:20 to 10:90 by weight.
Other Performance Additives
[0120] Compositions derived from the copolymer and/or lubricating
compositions described herein optionally further includes other
performance additives. The other performance additives comprise at
least one of metal deactivators, detergents, dispersants, viscosity
modifiers (other than the copolymer of the present invention),
friction modifiers, corrosion inhibitors, dispersant viscosity
modifiers (other than the copolymer of the present invention),
antiwear agents (other than the copolymer of the present
invention), extreme pressure agents (other than the copolymer of
the present invention), antiscuffing agents, antioxidants, foam
inhibitors, demulsifiers, pour point depressants, seal swelling
agents and mixtures thereof. Typically, fully-formulated
lubricating oil will contain one or more of these performance
additives.
Dispersants
[0121] Dispersants are often known as ashless-type dispersants
because, prior to mixing in a lubricating oil composition, they do
not contain ash-forming metals and they do not normally contribute
any ash forming metals when added to a lubricant and polymeric
dispersants. Ashless type dispersants 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 from which it is
derived in the range 350 to 5000, or 500 to 3000.
[0122] In one embodiment the invention further includes 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.
[0123] 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.
[0124] The dispersants may also be post-treated by conventional
methods by a reaction with any of a variety of agents. Among these
are boron compounds (such as boric acid), urea, thiourea,
dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones,
carboxylic acids such as terephthalic acid, hydrocarbon-substituted
succinic anhydrides, maleic anhydride, nitrites, epoxides, and
phosphorus compounds. In one embodiment the post-treated dispersant
is borated.
[0125] In one embodiment the dispersant may be a post treated
dispersant. The dispersant may be post treated with
dimercaptothiadiazole, optionally in the presence of one or more of
a phosphorus compound, a dicarboxylic acid of an aromatic compound,
and a borating agent.
[0126] In one embodiment the post treated dispersant may be formed
by heating an alkenyl succinimide or succinimide detergent with a
phosphorus ester and water to partially hydrolyze the ester. The
post treated dispersant of this type is disclosed for example in
U.S. Pat. No. 5,164,103.
[0127] In one embodiment the post treated dispersant may be
produced by preparing a mixture of a dispersant and a
dimercaptothiadiazole and heating the mixture above about
100.degree. C. The post treated dispersant of this type is
disclosed for example in U.S. Pat. No. 4,136,043.
[0128] In one embodiment the dispersant may be post treated to form
a product prepared comprising heating together: (i) a dispersant
(typically a succinimide), (ii) 2,5-dimercapto-1,3,4-thiadiazole or
a hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, or
oligomers thereof, (iii) a borating agent (similar to those
described above); and (iv) optionally a dicarboxylic acid of an
aromatic compound selected from the group consisting of 1,3 diacids
and 1,4 diacids (typically terephthalic acid), or (v) optionally a
phosphorus acid compound (including either phosphoric acid or
phosphorous acid), said heating being sufficient to provide a
product of (i), (ii), (iii) and optionally (iv) or optionally (v),
which is soluble in an oil of lubricating viscosity. The post
treated dispersant of this type is disclosed for example in
International Application WO 2006/654726 A.
[0129] Examples of a suitable dimercaptothiadiazole include
2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole. In several embodiments the number
of carbon atoms on the hydrocarbyl-substituent group includes 1 to
30, 2 to 25, 4 to 20, or 6 to 16. Examples of suitable
2,5-bis(alkyl-dithio)-1,3,4-thiadiazoles include
2,5-bis(tert-octyldithio)-1,3,4-thiadiazole
2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-decyl-dithio)-1,3,4-thiadiazole,
2,5-bis(tert-undecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-tridecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-tetradecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-pentadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-hexadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-heptadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-octadecyldithio)-1,3,4-thiadiazole,
2,5-bis(tert-nonadecyldithio)-1,3,4-thiadiazole or
2,5-bis(tert-eicosyldithio)-1,3,4-thiadiazole, or oligomers
thereof.
Detergents
[0130] The lubricant composition optionally further includes known
neutral or overbased detergents, i.e., ones prepared by
conventional processes known in the art. Suitable detergent
substrates include, phenates, sulphur containing phenates,
sulphonates, salixarates, salicylates, carboxylic acid, phosphorus
acid, alkyl phenol, sulphur coupled alkyl phenol compounds, or
saligenins.
Antioxidant
[0131] Antioxidant compounds are known and include sulphurised
olefins, diarylamine alkylated diarylamines, hindered phenols,
molybdenum dithiocarbamates, and mixtures thereof. Antioxidant
compounds may be used alone or in combination.
[0132] The hindered phenol antioxidant often contains a secondary
butyl and/or a tertiary butyl group as a sterically hindering
group. The phenol group is often further substituted with a
hydrocarbyl group and/or a bridging group linking to a second
aromatic group. Examples of suitable hindered phenol antioxidants
include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol,
4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol
or 4-butyl-2,6-di-tert-butylphenol, or
4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered
phenol antioxidant is an ester and may include, e.g., Irganox.TM.
L-135 from Ciba. Suitable examples of molybdenum dithiocarbamates
which may be used as an antioxidant include commercial materials
sold under the trade names such as Vanlube 822.TM. and Molyvan.TM.
A from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-Lube.TM. S-100,
S-165 and S-600 from Asahi Denka Kogyo K. K and mixtures
thereof.
[0133] The diarylamine alkylated diarylamine may be a
phenyl-.alpha.-naphthylamine (PANA), an alkylated diphenylamine, or
an alkylated phenylnapthylamine, or mixtures thereof. The alkylated
diphenylamine may include di-nonylated diphenylamine, nonyl
diphenylamine, octyl diphenylamine, di-octylated diphenylamine,
di-decylated diphenylamine, decyl diphenylamine and mixtures
thereof. In one embodiment the diphenylamine may include nonyl
diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl
diphenylamine, or mixtures thereof. In one embodiment the
diphenylamine may include nonyl diphenylamine, or dinonyl
diphenylamine. The alkylated diarylamine may include octyl,
di-octyl, nonyl, di-nonyl, decyl or di-decyl
phenylnapthylamines.
Viscosity Modifiers
[0134] The lubricating composition optionally further includes at
least one viscosity modifier other than the product of the present
invention. The viscosity modifier may include hydrogenated
styrene-butadiene rubbers, ethylene-propylene copolymers,
hydrogenated styrene-isoprene polymers, hydrogenated diene
polymers, polyalkyl styrenes, polyolefins, polyalkyl
(meth)acrylates, esters of maleic anhydride-styrene copolymers, or
mixtures thereof. In one embodiment the polymeric viscosity
modifier may be a poly(meth)acrylate, or mixtures thereof.
Antiwear Agent
[0135] The lubricating composition optionally further includes at
least one antiwear agent other than the product of the present
invention. Examples of suitable antiwear agents include oil soluble
amine salts of phosphorus compounds, sulphurised olefins, metal
dihydrocarbyldithiophosphates (such as zinc
dialkyldithiophosphates), thiocarbamate-containing compounds, such
as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers,
alkylene-coupled thiocarbamates, and
bis(S-alkyldithiocarbamyl)disulphides.
[0136] In one embodiment the oil soluble phosphorus amine salt
antiwear agent includes an amine salt of a phosphorus acid ester or
mixtures thereof. The amine salt of a phosphorus acid ester
includes phosphoric acid esters and amine salts thereof;
dialkyldithiophosphoric acid esters and amine salts thereof; amine
salts of phosphites; and amine salts of phosphorus-containing
carboxylic esters, ethers, and amides; and mixtures thereof. The
amine salt of a phosphorus acid ester may be used alone or in
combination.
[0137] In one embodiment the oil soluble phosphorus amine salt
includes partial amine salt-partial metal salt compounds or
mixtures thereof. In one embodiment the phosphorus compound further
includes a sulphur atom in the molecule. In one embodiment the
amine salt of the phosphorus compound is ashless, i.e., metal-free
(prior to being mixed with other components).
[0138] The amines which may be suitable for use as the amine salt
include primary amines, secondary amines, tertiary amines, and
mixtures thereof. The amines include those with at least one
hydrocarbyl group, or, in certain embodiments, two or three
hydrocarbyl groups. The hydrocarbyl groups may contain 2 to 30
carbon atoms, or in other embodiments 8 to 26, or 10 to 20, or 13
to 19 carbon atoms.
[0139] Primary amines include ethylamine, propylamine, butylamine,
2-ethylhexylamine, octylamine, and dodecylamine, as well as such
fatty amines as n-octylamine, n-decyl amine, n-dodecyl amine,
n-tetradecylamine, n-hex adecyl-amine, n-octadecylamine and
oleyamine. Other useful fatty amines include commercially available
fatty amines such as "Armeen.RTM." amines (products available from
Akzo Chemicals, Chicago, Ill.), such as Armeen C, Armeen O, Armeen
OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the letter
designation relates to the fatty group, such as coco, oleyl,
tallow, or stearyl groups.
[0140] Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine,
dihexylamine, diheptylamine, methylethylamine, ethylbutylamine and
ethylamylamine. The secondary amines may be cyclic amines such as
piperidine, piperazine and morpholine.
[0141] The amine may also be a tertiary-aliphatic primary amine.
The aliphatic group in this case may be an alkyl group containing 2
to 30, or 6 to 26, or 8 to 24 carbon atoms. Tertiary alkyl amines
include monoamines such as tert-butyl amine, tert-hexylamine,
1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine,
tertdodecylamine, tert-tetradecylamine, tert-hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, and
tert-octacosanylamine.
[0142] In one embodiment the phosphorus acid amine salt includes an
amine with C11 to C14 tertiary alkyl primary groups or mixtures
thereof. In one embodiment the phosphorus acid amine salt includes
an amine with C14 to C18 tertiary alkyl primary amines or mixtures
thereof. In one embodiment the phosphorus acid amine salt includes
an amine with C18 to C22 tertiary alkyl primary amines or mixtures
thereof.
[0143] Mixtures of amines may also be used in the invention. In one
embodiment a useful mixture of amines is "Primene.RTM. 81R" and
"Primene.RTM. JMT." Primene.RTM. 81R and Primene.RTM. JMT (both
produced and sold by Rohm & Haas) are mixtures of C11 to C14
tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary
amines respectively.
[0144] In one embodiment oil soluble amine salts of phosphorus
compounds include a sulphur-free amine salt of a
phosphorus-containing compound which is obtained/obtainable by a
process comprising: reacting an amine with either (i) a
hydroxy-substituted di-ester of phosphoric acid, or (ii) a
phosphorylated hydroxy-substituted di- or tri-ester of phosphoric
acid. A more detailed description of compounds of this type is
disclosed in International Application PCT/US08/051,126 (or
equivalent to U.S. application Ser. No. 11/627,405).
[0145] In one embodiment the hydrocarbyl amine salt of an
alkylphosphoric acid ester is the reaction product of a C14 to C18
alkyl phosphoric acid with Primene 81R.TM. (produced and sold by
Rohm & Haas) which is a mixture of C11 to C14 tertiary alkyl
primary amines.
[0146] Examples of hydrocarbyl amine salts of
dialkyldithiophosphoric acid esters include the reaction product(s)
of isopropyl, methyl-amyl (4-methyl-2-pentyl or mixtures thereof),
2-ethylhexyl, heptyl, octyl or nonyl dithiophosphoric acids with
ethylene diamine, morpholine, or Primene 81R.TM., and mixtures
thereof.
[0147] In one embodiment the dithiophosphoric acid may be reacted
with an epoxide or a glycol. This reaction product is further
reacted with a phosphorus acid, anhydride, or lower ester. The
epoxide includes an aliphatic epoxide or a styrene oxide. Examples
of useful epoxides include ethylene oxide, propylene oxide, butene
oxide, octene oxide, dodecene oxide, and styrene oxide. In one
embodiment the epoxide is propylene oxide. The glycols may be
aliphatic glycols having from 1 to 12, or from 2 to 6, or 2 to 3
carbon atoms. The dithiophosphoric acids, glycols, epoxides,
inorganic phosphorus reagents and methods of reacting the same are
described in U.S. Pat. Nos. 3,197,405 and 3,544,465. The resulting
acids may then be salted with amines. An example of suitable
dithiophosphoric acid is prepared by adding phosphorus pentoxide
(about 64 grams) at 58.degree. C. over a period of 45 minutes to
514 grams of hydroxypropyl
O,O-di(4-methyl-2-pentyl)phosphorodithioate (prepared by reacting
di(4-methyl-2-pentyl)-phosphorodithioic acid with 1.3 moles of
propylene oxide at 25.degree. C.). The mixture is heated at
75.degree. C. for 2.5 hours, mixed with a diatomaceous earth and
filtered at 70.degree. C. The filtrate contains 11.8% by weight
phosphorus, 15.2% by weight sulphur, and an acid number of 87
(bromophenol blue).
[0148] The dithiocarbamate-containing compounds may be prepared by
reacting a dithiocarbamate acid or salt with an unsaturated
compound. The dithiocarbamate containing compounds may also be
prepared by simultaneously reacting an amine, carbon disulphide and
an unsaturated compound. Generally, the reaction occurs at a
temperature from 25.degree. C. to 125.degree. C.
[0149] Examples of suitable olefins that may be sulphurised to form
an the sulphurised olefin include propylene, butylene, isobutylene,
pentene, hexane, heptene, octane, nonene, decene, undecene,
dodecene, undecyl, tridecene, tetradecene, pentadecene, hexadecene,
heptadecene, octadecene, octadecenene, nonodecene, eicosene or
mixtures thereof. In one embodiment, hexadecene, heptadecene,
octadecene, octadecenene, nonodecene, eicosene or mixtures thereof
and their dimers, trimers and tetramers are especially useful
olefins. Alternatively, the olefin may be a Diels-Alder adduct of a
diene such as 1,3-butadiene and an unsaturated ester such as butyl
acrylate.
[0150] Another class of sulphurised olefin includes fatty acids and
their esters. The fatty acids are often obtained from vegetable oil
or animal oil; and typically contain 4 to 22 carbon atoms. Examples
of suitable fatty acids and their esters include triglycerides,
oleic acid, linoleic acid, palmitoleic acid or mixtures thereof.
Often, the fatty acids are obtained from lard oil, tall oil, peanut
oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures
thereof. In one embodiment fatty acids and/or ester are mixed with
olefins.
[0151] In an alternative embodiment, the antiwear agent may be a
monoester of a polyol and an aliphatic carboxylic acid as described
above. In one embodiment the monoester of a polyol and an aliphatic
carboxylic acid may include glycerol monooleate, or mixtures
thereof.
Antiscuffing Agent
[0152] The lubricant composition may also contain an antiscuffing
agent. Antiscuffing agent compounds are believed to decrease
adhesive wear and are often sulphur containing compounds. Typically
the sulphur containing compounds include sulphurised olefins,
organic sulphides and polysulphides, such as dibenzyldisulphide,
bis-(chlorobenzyl)disulphide, dibutyl tetrasulphide, di-tertiary
butyl polysulphide, sulphurised methyl ester of oleic acid,
sulphurised alkylphenol, sulphurised dipentene, sulphurised
terpene, sulphurised Diels-Alder adducts, alkyl sulphenyl
N'N-dialkyl dithiocarbamates, the reaction product of polyamines
with polybasic acid esters, chlorobutyl esters of
2,3-dibromopropoxyisobutyric acid, acetoxymethyl esters of dialkyl
dithiocarbamic acid and acyloxyalkyl ethers of xanthogenic acids
and mixtures thereof.
Extreme Pressure Agents
[0153] Extreme Pressure (EP) agents that are soluble in the oil
include sulphur- and chlorosulphur-containing EP agents,
chlorinated hydrocarbon EP agents and phosphorus EP agents.
Examples of such EP agents include chlorinated wax; sulphurised
olefins (such as sulphurised isobutylene), organic sulphides and
polysulphides such as dibenzyldisulphide,
bis-(chlorobenzyl)disulphide, dibutyl tetrasulphide, sulphurised
methyl ester of oleic acid, sulphurised alkylphenol, sulphurised
dipentene, sulphurised terpene, and sulphurised Diels-Alder
adducts; phosphosulphurised hydrocarbons such as the reaction
product of phosphorus sulphide with turpentine or methyl oleate;
phosphorus esters such as the dihydrocarbon and trihydrocarbon
phosphites, e.g., dibutyl phosphite, diheptyl phosphite,
dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl
phosphite, tridecyl phosphite, distearyl phosphite and
polypropylene substituted phenol phosphite; metal thiocarbamates
such as zinc dioctyldithiocarbamate and barium heptylphenol diacid;
amine salts of alkyl and dialkylphosphoric acids or derivatives
including, for example, the amine salt of a reaction product of a
dialkyldithiophosphoric acid with propylene oxide and subsequently
followed by a further reaction with P.sub.2O.sub.5; and mixtures
thereof (as described in U.S. Pat. No. 3,197,405).
[0154] Corrosion inhibitors that may be useful in the compositions
of the invention include fatty amines, octylamine octanoate,
condensation products of dodecenyl succinic acid or anhydride and a
fatty acid such as oleic acid with a polyamine.
[0155] Foam inhibitors that may be useful in the compositions of
the invention include copolymers of ethyl acrylate and
2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers
including tri alkyl phosphates, polyethylene glycols, polyethylene
oxides, polypropylene oxides and (ethylene oxide-propylene oxide)
polymers.
[0156] Pour point depressants that may be useful in the
compositions of the invention include polyalphaolefins, esters of
maleic anhydride-styrene copolymers, poly(meth)acrylates,
polyacrylates or polyacrylamides.
[0157] As used herein the term "fatty alkyl" or "fatty" in relation
to friction modifiers means a carbon chain having 10 to 22 carbon
atoms, typically a straight carbon chain.
[0158] Friction modifiers that may be useful in the compositions of
the invention include fatty acid derivatives such as fatty amines,
esters, epoxides, fatty imidazolines, condensation products of
carboxylic acids and polyalkylene-polyamines and amine salts of
alkylphosphoric acids, fatty phosphonate esters and reaction
products from fatty carboxylic acids reacted with guanidine,
aminoguanidine, urea, thiourea, and salts thereof.
INDUSTRIAL APPLICATION
[0159] The method and lubricating composition of the invention may
be utilised in refrigeration lubricants, greases, gear oils, axle
oils, drive shaft oils, traction oils, manual transmission oils,
automatic transmission oils, metal working fluids, hydraulic oils,
or internal combustion engine oils. The gear oils, axle oils, drive
shaft oils, manual transmission oils, automatic transmission oils
may be collectively referred to as being used as part of a
driveline device.
[0160] In one embodiment the method and lubricating composition of
the invention may be for at least one of gear oils, axle oils,
drive shaft oils, traction oils, manual transmission oils or
automatic transmission oils.
[0161] An automatic transmission includes continuously variable
transmissions (CVT), infinitely variable transmissions (IVT),
toroidal transmissions, continuously slipping torque converter
clutches (CSTCC), stepped automatic transmissions or dual clutch
transmissions (DCT).
[0162] The gear oil or axle oil may be used in a planetary hub
reduction axle, a mechanical steering and transfer gear box in a
utility vehicle, a synchromesh gear box, a power take-off gear, a
limited slip axle, and a planetary hub reduction gear box.
[0163] In one embodiment the copolymer of the invention in an axle
oil provides antifoam performance.
[0164] In several embodiments a suitable lubricating composition
includes the copolymer present (on an actives basis) in ranges as
shown in the following table.
TABLE-US-00004 TABLE wt % of wt % of Other wt % of Oil of Copolymer
of the Performance Lubricating Embodiments Invention Additives
Viscosity A 0.1-70 0.5-20 10-99.4 B 1.5-65 0.5-15 20-98 C 10-60
0.5-15 25-89.5 D 15-60 0.5-15 25-84.5 E 18-46 0.5-15 39-81.5
[0165] In different embodiments the copolymer of the invention may
be present at 0.1 wt % to 99.9 wt %, or 1 wt % to 70 wt %, or 1.5
wt % to 65 wt %, or 10 wt % to 60 wt %, or 15 wt % to 60 wt %, or
18 wt % to 46 wt %.
[0166] 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
Polymer Intermediate 1
[0167] A 5 L flange flask is charged with 353 g of maleic
anhydride, 606 g of 1-dodecene, and toluene (2372.8 g). The flask
is fitted with a flange lid and clip, PTFE stirrer gland, rod and
overhead stirrer, water-cooled condenser, thermocouple and nitrogen
inlet. The flask is stirred under nitrogen. Trigonox.RTM.21S and
toluene (315 g) are charged to a conical flask with side-arm and
nitrogen is applied. The flask is heated to 105.degree. C. The
contents of the conical flask are charged to the flange flask via
Masterflex.TM. pump (flow rate=1.2 ml/min.sup.-1) over a period of
5 hours. The flask is cooled to 50.degree. C. A Dean-Stark trap is
fitted to the flask and the flask is heated to 120.degree. C. to
remove toluene before alcohol addition. The flask is cooled to
110.degree. C. Alfol.RTM.810 (417.6 g) and Tsofol.RTM.16
(2-hexyl-1-decanol, 174 g) are mixed and charged to the flask over
1.5 hours via dropping funnel. Alfol 810 (522 g) and
methanesulphonic acid (24.7 g) are mixed together and charged to
the flask via dropping funnel over 1.5 hours whilst heating to
145.degree. C. The flask is stirred for 2 hours before cooling to
ambient. The flask is heated to 145.degree. C. The flask is stirred
for a further 8 hours. A second methanesulphonic acid addition
(12.4 g) is charged to the flask. A butanol addition (55.7 g) is
then charged to the flask and stirred for 18 hours. A 2nd butanol
addition is charged to the flask and stirred for 3 hours. A 3rd
butanol addition is charged to the flask and stirred for 2.5 hours.
A 4th butanol addition is charged to the flask and stirred for 18
hours. A 5th butanol addition is charged to the flask and stirred
for 3 hours. A 6th butanol addition is charged to the flask and
stirred for 3 hours. 16.82 g of sodium hydroxide (50 mol % in
water) is charged to the flask whilst heating to 150.degree. C. and
left to stir for a further 45 minutes. 7.56 g of
dimethylaminopropylamine (to deliver 0.1% nitrogen to the
copolymer) is charged to the flask and then stirred for 2 hours.
The apparatus is arranged for vacuum distillation. The flask is
heated to 100.degree. C. and vacuum is applied and held for 30
minutes. The flask is heated to 130.degree. C. and held for 45
minutes. The flask is then heated to 150.degree. C. and held for a
further 3 hours. The flask is then cooled to 100.degree. C. and
vacuum removed. The product is filtered through diatomaceous earth
to afford the desired ester copolymer having approx 0.1% N, 2 mg
KOH/g TBN.
Polymer Intermediate 2
[0168] Ester copolymer 2 (Esc2) is prepared using the general
procedure outlined above using 3-morpholinopropan-1-amine to
deliver 0.12% nitrogen, 2.2 mg KOH/g TBN in place of
dimethylaminopropylamine.
Polymer Intermediate 3
[0169] Ester copolymer 3 (Esc3) is prepared using the general
procedure outlined above using dimethylaminopropylamine to deliver
0.27% nitrogen, 4.8 mg KOH/g TBN.
Polymer Intermediate 4
[0170] Ester copolymer 2 (Esc2) is prepared using the general
procedure outlined above using 3-morpholinopropan-1-amine to
deliver 0.25% nitrogen, approx 5 mg KOH/g TBN, in place of
dimethylaminopropylamine.
Polymer Intermediate 5
[0171] Ester copolymer 3 (Esc3) is prepared using the general
procedure outlined above dimethylaminopropylamine to deliver 5.6 mg
KOH/g TBN.
Polymer Intermediate 6
[0172] Ester copolymer 5 (Esc5) is prepared using the general
procedure outlined above using dimethylaminopropylamine to deliver
0.4% nitrogen, approx 8 mg KOH/g TBN.
Polymer Intermediate 7
[0173] Ester copolymer 2 (Esc2) is prepared using the general
procedure outlined above using 3-morpholinopropan-1-amine to
deliver 0.4% nitrogen, approx 8 mg KOH/g TBN, in place of
dimethylamino-propylamine.
Phosphate Intermediate 1
[0174] A 250 ml 3 neck round bottom flask is charged with
isooctanol (137.4 g) and the flask is fitted with thermocouple,
magnetic follower, and nitrogen inlet (250 cm.sup.3/min), and the
alcohol is warmed to 50.degree. C. and stirred. A screw feed
addition funnel (dried for 24 hours at 100.degree. C.) is charged
with phosphorus pentoxide (50 g) under a nitrogen blanket. The
screw feed addition funnel is added to flask and phosphorus
pentoxide is added over approx 1 hours maintaining the temperature
between 50 to 58.degree. C. The reaction flask is warmed to
90.degree. C. and stirred for 5 hours and cooled to ambient
temperature. The product has a TAN of 305.8 mg KOH/g.
Phosphate Intermediate 2
[0175] A 500 ml flange flask is fitted with overhead stirrer, water
cooled condenser, screw feeder equipped with phosphorus pentoxide
(81.88 g), a thermocouple, and a nitrogen inlet (250 cm.sup.3/min).
The flask is charged with isooctanol (150 g) and 1,2-propanediol
(43.90 g) and stirred at 300 rpm and warmed to 60.degree. C.
Phosphorus pentoxide is added to maintain the temperature 60 to
70.degree. C. over 1 hour. The reaction mixture is warmed to
90.degree. C. and held for 5 hours. The reaction mixture is cooled
to 70.degree. C. and held under vacuum (1 kPa or 10 mbar) for 3
hours. A light brown, clear fluid is obtained. The product has a
TAN of 216.0 mg KOH/g.
Phosphate Intermediate 3
[0176] A 500 mL 3-necked round bottom flask is equipped with
magnetic stirrer, thermocouple and solid addition hopper with a
2-neck adaptor with nitrogen purge line and a bubbler to keep the
system under a constant nitrogen blanket. Oleyl glycolate (200.21
g) is charged to the flask and heated to 60.degree. C. with
stirring. Phosphorus pentoxide (58.76 g) is added to the solid
addition hopper and packed down under the nitrogen blanket. The
phosphorus pentoxide is then added slowly over 3 hours, controlling
the exotherm to keep the temperature of the reaction between
55.degree. C. and 65.degree. C. The reaction is then left to cool
overnight with a nitrogen purge. The next day the mixture is heated
to 70.degree. C. with stirring for 5 hours and cooled to room
temperature affording the desired phosphate intermediate. The
product has a TAN of 165.0 mg KOH/g.
Phosphate Intermediate 4
[0177] 2-ethylhexyl glycolate (39.44 g) is charged to 250 ml
3-necked round bottom flask fitted, magnetic follower, solid
addition hopper charged with phosphorus pentoxide (9.93 g) under
nitrogen. The 2-ethylhexyl glycolate is warmed to 60.degree. C. and
phosphorus pentoxide is added at such a rate as to maintain the
temperature below 65.degree. C. for 40 minutes. The reaction
mixture is heated to 60.degree. C. before heating to 70.degree. C.
and held for 2 hours. The product is a pale red/brown viscous oil.
The product has a TAN of 201.6 mg KOH/g.
Phosphate Intermediate 5
[0178] all glassware is dried at 100.degree. C. for 48 hours and
constructed under nitrogen whilst hot. C.sub.11-14 dialkyl tartrate
(175 g) is charged to 500 ml 3-necked round bottom flask fitted
with thermocouple, magnetic follower, solid addition hopper charged
with phosphorus pentoxide (29.8 g) under nitrogen. The flask
contents are stirred at 100 rpm at 55.degree. C. and when at
temperature the phosphorus pentoxide is added at such a rate as to
maintain the temperature below 65.degree. C. over a period of 40
minutes. The reaction mixture is heated to 60.degree. C. and held
for 4 hours before heating 70.degree. C. and held for 2 hours. The
reaction mixture is cooled and a pale red/brown viscous oil is
obtained. The product has TAN 96 mg KOH/g.
Phosphate Intermediate 5a
[0179] all glassware is dried at 100.degree. C. for 48 hours and
constructed under nitrogen whilst hot. C.sub.11-14 dialkyl tartrate
(293.3 g) is charged to 500 ml 3-necked round bottom flask fitted
with thermocouple, magnetic follower, solid addition hopper charged
with phosphorus pentoxide (50 g) under nitrogen. The flask contents
are stirred at 100 rpm at 50.degree. C. and when at temperature the
phosphorus pentoxide is added at such a rate as to maintain the
temperature below 60.degree. C. over a period of 40 minutes. The
reaction mixture is heated to 50.degree. C. and held for 18 hours
before heating 70.degree. C. and held for 1 hour. The reaction
mixture is cooled and a pale red/brown viscous oil is obtained. The
product has TAN 92.2 mg KOH/g.
Phosphate Intermediate 6
[0180] all glassware is dried at 100.degree. C. for 48 hours and
constructed under nitrogen whilst hot. C.sub.11-14 dialkyl tartrate
(255.51 g) is charged to 1 L flange flask fitted with thermocouple,
water cooled condenser topped with bubbler, N.sub.2 inlet at 100
cm.sup.3/min, and pressure equalising dropping funnel containing
poly phosphoric acid, and the other port is blocked with a glass
stopper. The dialkyl tartrate is warmed to 55.degree. C. and
stirred at 250 rpm at 55.degree. C., and polyphosphoric acid (52.3
g) is added at such a rate as to maintain the temperature below
65.degree. C. over a period of 30 minutes. The reaction mixture is
heated to 60.degree. C. for 4 hours and held for 4 hours. The flask
is then heated to 70.degree. C. and held for 2 hours. The product
is a pale red/brown viscous oil. The product has a TAN (bromophenol
blue) 120.0 mg KOH/g.
Phosphate Intermediate 7
[0181] A 500 ml flange flask is fitted with overhead stirrer, water
cooled condenser, screw feeder equipped charged with phosphorus
pentoxide (81.88 g), and a thermocouple. Isooctanol (225 g) is
charged to the flask and stirred at 300 rpm and warmed to
60.degree. C. Phosphorus pentoxide is added to maintain the
temperature of 58 to 58.degree. C. for a period of 1 hour. The
reaction mixture is warmed to 90.degree. C. and held for 5 hours
and cooled to 38.degree. C. and propylene oxide (55.60 g) is added
subsurface over 1.5 hour and stirred for 2 hours. The flask is then
cooled to 50.degree. C. and phosphorus pentoxide (47.5 g) is added
via screwfeeder over 1 hour. The flask is then heated to 90.degree.
C. and held with stirring for 5 hours. The flask is then cooled to
ambient. The product is a coloured viscous liquid. The product has
a TAN (bromophenol blue) of 180 mg KOH/g.
Phosphate Intermediate 8
[0182] A 500 ml flask is charged with glycerol monooleate (356.54
g), and iso-octanol (1130 g). The flask is fitted with a flange lid
and clip, PTFE stirrer gland, rod and overhead stirrer,
thermocouple, water-cooled condenser, nitrogen inlet port and
powder dropping funnel. The flask is heated to 50.degree. C. with
stirring at 350 rpm. Phosphorus pentoxide (141.9 g) is charged to
the dropping funnel under N.sub.2 and then charged to the flask
over one hour. The temperature is kept below 60.degree. C. The
flask is stirred at 50.degree. C. for 18 hours. Vacuum (20-40 mbar)
is applied to the reaction mixture for 2 hours to remove volatile
components and the phosphate intermediate is then cooled to room
temperature.
Final Product 1
[0183] phosphate intermediate 1 (20.10 g) is added to polymer
intermediate 2 (2000 g) at 70.degree. C. with stirring (250 rpm)
under nitrogen and stirred for 2.5 hours. The desired product is
isolated as a pale yellow, clear viscous liquid.
Final Product 2
[0184] phosphate intermediate 2 (20.29 g) is added to polymer
intermediate 2 at 70.degree. C. with stirring (250 rpm) under
nitrogen and stirred for 1.5 hours. The product is isolated as a
pale yellow, clear viscous liquid.
Final Product 3
[0185] phosphate intermediate 3 (26.5 g) is added to polymer
intermediate 1 at 70.degree. C. with stirring (250 rpm) under
nitrogen and stirred for 1.5 hours. The product is isolated as a
pale yellow, clear viscous liquid.
Final Product 3
[0186] A 5 litre flange flask is fitted with PTFE gasket, flange
lid, nitrogen inlet 200 cm.sup.3/min, thermocouple, overhead
stirrer with PTFE gland and double wall water cooled condenser. The
flask is charged with polymer intermediate 2 (2065.6 g) and warmed
to 70.degree. C. and stirred at 350 rpm. The flask is charged with
phosphate intermediate 4 (22.8 g). The charge takes approximately 5
minutes. The reaction contents are stirred for 7 hours at
70.degree. C. and cooled to room temperature to afford a pale
coloured viscous oily product.
Final Product 4
[0187] A 5 litre flange flask is fitted with PTFE gasket, flange
lid, nitrogen inlet (200 cm.sup.3/min), thermocouple, overhead
stirrer with PTFE gland and fitted with double wall water cooled
condenser. The flask is charged with polymer intermediate 1
(3597.62 g) and the Phosphate Intermediate 5a (79.8 g) and stirred
at 250 rpm, warming to 70.degree. C. and held for 18 hours. The
product is cooled to afford the desired product as a pale yellow
viscous oil.
Final Product 5
[0188] A 5 litre flange flask is fitted with PTFE gasket, flange
lid, nitrogen inlet (200 cm.sup.3/min), thermocouple, overhead
stirrer with PTFE gland and fitted with double wall water cooled
condenser. The flask is charged with polymer intermediate 3
(4079.54 g) and phosphate intermediate 5 (203.01 g) and stirred at
300 rpm, warming to 70.degree. C. and hold for 20 hours. The
product is cooled to room temperature to afford a pale yellow
viscous oil.
Final Product 6
[0189] A 5 litre flange flask is fitted with PTFE gasket, flange
lid, nitrogen inlet (200 cm.sup.3/min), thermocouple, overhead
stirrer with PTFE gland and fitted with double wall water cooled
condenser. The flask is charged with polymer intermediate 3 (3000
g) and phosphate intermediate 6 (119 g) and stirred at 300 rpm,
warmed to 80.degree. C. and held for 4 hours. The product is cooled
to room temperature to afford a pale yellow viscous oil.
Final Product 7
[0190] O,O-bis(4-methylpentan-2-yl) S-hydrogen phosphorodithioate
(22.09 g, TAN 198.1 mg KOH/g) is added to polymer intermediate 2 at
70.degree. C. over 20 minutes with stirring (250 rpm) under
nitrogen and stirred for 4 hours. The product is isolated as a pale
yellow, clear viscous liquid.
Final Product 8
[0191] to a 5 l flange flask fitted with overhead stirrer, nitrogen
inlet (200 cm.sup.3/min), water cooled condenser and thermocouple
is added polymer intermediate 3 (1000 g), C12-14 dialkyl tartrate
(31.76 g) and 115% polyphosphoric acid (21.69 g). The reaction
mixture is stirred at 300 rpm and warmed to 80.degree. C. The
reaction mixture is stirred for 1 hour and isooctanol (29.83 g) is
added and stirred for 17 hours. To the reaction mixture is added
polymer intermediate (2000 g) over 40 minutes, stirred 3 hours and
cooled to room temperature to afford final product 8 as a viscous
oil.
Final Product 9
[0192] Polymer intermediate 5 (25278 g) is stirred at 167 rpm,
under 0.2 kg/h N.sub.2 for 1 hours and C12-14 dialkyl tartrate
(576.55 g) is added in one portion. Then the reactants are stirred
overnight and polyphosphoric acid (190.89 g) is charged via manway.
Stir 30 minutes and heat to 80.degree. C. and stir for 4.5 hours.
Butanol (83.01 g) is added via sampling pot, rinsed pot several
times with reaction mixture and stirred 50 minutes, heat to
100.degree. C. Stir for 1.75 hours and cool to room temperature.
The reaction mixture is filtered through diatomaceous earth (180 g)
at 85.degree. C. for 30 minutes and increase to 100.degree. C. for
45 minutes. The product is a viscous amber oil.
Final Product 10
[0193] phosphate intermediate 7 (24.29 g) is added to polymer
intermediate 6 (2000 g) at 70.degree. C. with stirring (250 rpm)
under nitrogen and stirred for 1.5 hours. The desired product is
isolated as a pale yellow, clear viscous liquid, Yield: 2024 g.
Final Product 11
[0194] phosphate intermediate 5 (47.4 g) is added to polymer
intermediate 2 (2000 g) at 70.degree. C. with stirring (250 rpm)
under nitrogen and stirred for 3 hours. The product is a dark brown
viscous oil.
Study 1: Manual Transmission Lubricant with about 300 ppm
Phosphorus
[0195] Comparative manual transmission lubricant 1 (CMTL1) contains
75.2 wt % PAO-4 (polyalphaolefin 4 mm.sup.2/s (cSt)) base oil, 18.8
wt % of a viscosity modifier of Polymer intermediate 2 (i.e., a
polymer that has not been phosphated), 0.35 wt % of a phosphorus
antiwear agent, and the balance to 100 wt % of other conventional
manual transmission lubricant additives. The lubricant has a
phosphorus level of 310 ppm.
[0196] Inventive manual transmission lubricant 1 (IMTL1) contains
75.2 wt % PAO-4 (polyalphaolefin 4 mm.sup.2/s (cSt)) base oil, 19.0
wt % of a viscosity modifier based on the product of final product
2, 0.075 wt % of a phosphorus antiwear agent, and the balance to
100 wt % of other conventional manual transmission lubricant
additives. The lubricant has a phosphorus level of 296 ppm.
[0197] CMTL1 and IMTL1 are evaluated by the methodology of ASTM
Method D4172 (4-ball wear test), and FZG A10/16.6R/90 spur gear
scuffing evaluation. The results obtained are as follows:
TABLE-US-00005 CMTL1 IMTL1 4 ball wear scar (mm) 0.453 0.344 FZG
revolutions at point of failure 7956 21,700 (Load stage 6) Weight
loss pin (mg) 213 114 Weight loss of wheel (mg) 302 148
[0198] The results indicate that the lubricating composition of the
present invention has reduced wear in the 4 ball wear test and has
prolonged durability in the FZG, indicating improved scuffing and
wear resistance.
Study 2: Manual Transmission Lubricant with about 500 ppm
Phosphorus
[0199] Comparative manual transmission lubricant 2 (CMTL2) contains
75.8 wt % PAO-4 (polyalphaolefin 4 mm.sup.2/s (cSt)) base oil, 18.8
wt % of a viscosity modifier based of Polymer intermediate 2, 0.6
wt % of a phosphorus antiwear agent, and the balance to 100 wt % of
other conventional manual transmission lubricant additives. The
lubricant has a phosphorus level of 532 ppm.
[0200] Inventive manual transmission lubricant 2 (IMTL2) contains
76.1 wt PAO-4 (polyalphaolefin 4 mm.sup.2/s (cSt)) base oil, 18.8
wt % of a viscosity modifier based on the product of final product
11, 0.3 wt % of a phosphorus antiwear agent, and the balance to 100
wt % of other conventional manual transmission lubricant additives.
The lubricant has a phosphorus level of 499 ppm.
[0201] CMTL2 and IMTL2 are evaluated by the methodology of ASTM
Method D4172 (4-ball wear test). The results obtained are:
TABLE-US-00006 CMTL2 IMTL2 4 ball wear scar (mm) 0.464 0.349
[0202] The results indicate that that the lubricating composition
of the present invention has reduced wear in the 4 ball wear test
when phosphorus content of the lubricant is about 500 ppm.
Study 3: Automotive Gear Oil with about 800 ppm Phosphorus
[0203] Comparative automotive gear oil 1 (CAG1) contains 49.3 wt %
PAO-4 (polyalphaolefin 4 mm.sup.2/s (cSt)) base oil, 46 wt % of a
viscosity modifier of Intermediate Polymer 2, 1 wt % of a
phosphorus antiwear agent described in above, and the balance to
100 wt % of other automotive gear oil lubricant additives. The
lubricant has a phosphorus level of 839 ppm.
[0204] Inventive automotive gear oil 1 (IAG1) contains 49.9 wt %
PAO-4 (polyalphaolefin 4 mm.sup.2/s (cSt)) base oil, 46 wt % of a
viscosity modifier of Final Product 4, 0.4 wt % of a phosphorus
antiwear agent described in [0112] above, and the balance to 100 wt
% of other conventional manual transmission lubricant additives.
The lubricant has a phosphorus level of 788 ppm.
[0205] CAG1 and IAG1 are evaluated for the capability for
load-carrying, wear, and extreme pressure properties in a hypoid
axle under conditions of low-speed, high-torque operation using
ASTM method D6121-05a. The results obtained are presented in the
table below.
[0206] The results in the table below indicate an automotive gear
oil lubricant containing the composition of the present invention
overall has reduced wear in ring and pinion. In particular,
reduction in wear observed in ring gear ridging and pinion gear
pitting/spalling.
TABLE-US-00007 ASTM D6121-05a Rating Parameter Rated CAG1 IAG1 Ring
Gear Final Wear Rating 7 7 Final Surface Fatigue Rippling 10 10
Final Surface Fatigue Ridging 9 10 Final Surface Fatigue Pitting
and Spalling Merit 9.9 9.9 Final Surface Fatigue Scoring 10 10 Wear
Pinion Gear Final Rating 8 6 Final Rippling 9 9 Final Ridging 9 9
Final Scoring 9.3 9.8 Final Pitting and Spalling Merit 10 10
[0207] It is known that some of the materials described above may
interact in the final formulation, so that the components of the
final formulation may be different from those that are initially
added. The products formed thereby, including the products formed
upon employing lubricant composition of the present invention in
its intended use, may not be susceptible of easy description.
Nevertheless, all such modifications and reaction products are
included within the scope of the present invention; the present
invention encompasses lubricant composition prepared by admixing
the components described above.
[0208] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: hydrocarbon substituents,
including aliphatic, alicyclic, and aromatic substituents;
substituted hydrocarbon substituents, that is, substituents
containing non-hydrocarbon groups which, in the context of this
invention, do not alter the predominantly hydrocarbon nature of the
substituent; and hetero substituents, that is, substituents which
similarly have a predominantly hydrocarbon character but contain
other than carbon in a ring or chain. A more detailed definition of
the term "hydrocarbyl substituent" or "hydrocarbyl group" is
described in paragraphs [0137] to [0141] of published application
US 2010-0197536.
[0209] 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.
[0210] Each of the documents referred to above is incorporated
herein by reference. 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.
[0211] While the invention has been explained in relation to its
preferred embodiments, 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.
* * * * *