Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
Case 3994
LUBRICATING OIL DISPERSANT
A large percentage of today's automobiles are used
in city stop-and-go driving where the engines do not reach
their most efficient opera~ing temperatures. Large amounts
of partial oxidation products are formed and reach the
crankcase of the engine by blowing past the piston rings.
These partial oxidation products react with oil in the
crankcase and lead to the formation of deposits on various
operating parts of engines, resultlng in sludge and I ~;
varnish. Other deposits and organic acids result from
deterioration of the oil itself. To prevent deposition of
these materials on various engine parts, it is necessary
to incorporate dispersants in the lubricating oil compositions,
thus keeping these polymeric products highly dispersed in
a condition unfavorable for deposition on metals. '~
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For the most part, the various dispersants which
have been used to efectively disperse the precursors of
sludges and varnishes are metal organic compounds such as
calcium alkaryl-sulfonate. These dispersants also neutralize
to some extent the organic acids, and thereby help prevent
corrosion of the engine parts. However, such dispersants
have the disadvantage of formlng ash deposits in the engine,
which deposits lower engine performance by fouling spark
plugs and valves and by contributing to preignition.
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SUMM~RY _ ~q~39
According to the present invention, lubricating
oil compositions are provided having good dispexsant activity
and improved wear and anticorrosion properties. This is
accomplished by adding a small but effective amount of the
produc made by heating a mixture of sulfur with a condensation
product of a high molecular weight alkylsubstituted phenol, a
reactive amine and an aldehyde.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A preferred embodiment of this invention i9 a product
made by the process comprising heating to a temperature of about
50-300DC. a mixture of (1) from about 1-20 parts by weight of
sulfur and (2) about 100 parts by weight of a condensation product
made by reacting about (a) one mole part o a high molecular
weight alkylphenoL wherein said alkyl has a molecular weight of ~ ;~
from about 600-3000, (b) about 0.1-10 mole parts of an amine
selected rom aliphatic amines containing from 1 to about 20
carbon atoms and having at }east one~ NH group, morpholine and ,~
piperidive-and (c) about 0.1-10 mole parts of an aliphatic
aldehyde containing from 1 to about 6 carbon atoms.
The condensation product of a phenol, formaldehyde
and a reactive amine is known as a Mannich condensation product.
- The Mannich condensation products used in making the present
additives are known. They are described in Otto, U.S. 3,368,972,
. and Worrel, U.S. 3,413,347.
The preferred alkylphenols used to prepare the Mannich
product are the polyolefin-substituted phenols which are readily
made by alkylating phenol with a polyolefin having an average ~ ~
molecular weight of about 600-3000 using a BF3 phenate catalyst. ; ~ ~`
~he preferred polyolefins are polymers of
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C2-10 olefins such as eth ene, propylene, butene, isobute~e,
octene-l, isooctene, decene-l, and the like. The more pre~erred
polyolefin-substituted phenols are polypropylene and polybutene~
substituted phenols in which the polypropylene or polybutene
substituents have an average molecular weight of about 600-3000,
and more preferably 750-1500. A particularly preferred phenol
is a polyisobutene-substituted phenol in which the polyIso~
butene group has a molecular weight of 750-1500.
The aliphatic amine can be any aliphatic amine
containing at least one ~ NH group capable of entering into
a Mannich condensation reaction. Preferably, the amine is
an aliphatic amine containing 1 to about 20 carbon atoms
such as methylamine, dimethylamine, ethylamine, diethylamine,
n-propylamine, n-butylamine, isobutylamine, sec-butylamine, ;
n-hexylamine, 2-ethylhexylamine, laurylamine, oleylamine,
stearylamine, eicosylamine, and the like.
One preferred class of amines is the alkylenepoly~
amines, in particular, ethylenepolyamines. These amines
are fully described in Kirk-Othmer, "Encyclopedia of
Chemical Technology," Vol. 5, p. 898~905. They can be `~
represented by the following ormula~
H2N ~ CH2~CH2N~I ~x
wherein x is an integer from 1 tv about 6. They can be used
individually but are preferably used as mixtures. One such
mixture is marketed commercially by Union Carbide Chemical
Company as "Polyamine H" (trade name). Examples of the
ethylene-polyamines are ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, and the like,
lncluding mixtures thereof.
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Another preferred class of useful amines is the
N,N-dialkyl-alkanediamines. PreEerably, the N-alkyl
groups contain from 1 to about 6 carbon atoms and the
divalent alkane group contains from 2 to about 6 carbon
atoms. Examples of these are N,N-dimethyl-ethylenediamine,
N,N-diethyl-1,3-propanediamine, N,N-dimet:hyl-1,3-propane~
diamine, N,N-diisobutyl- 1,6-hexanediamirle, N,N-dimethyl-
1,6-hexanediamine, N,N-di-_-hexyl-1,4-butanediamine, N-
methyl-N-hexyl-1,3-propanediamine, and the like. Of these,
the most preferred is N,N-dimethyl-1,3-propanediamine.
The aldehyde reactant can be any aldehyde con~
taining from 1 to about 6 carbon atoms such as formaldehyde,
acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, ~ ;
hexaldehyde, and the like. The more preferred aldehyde
reactants are the low molecular weight aliphatic aldehydes
containing from 1 to about 4 carbon atoms such as formaldehyde, ~
acetaldehyde, butyraldehyde, isobutyraldehyde, and the like. ~ ~ .
The most preferred aldehyde is formaldehydeJ which may
be used in its monomeric or polymeric form such as para-
formaldehyde.
The mole ratio of the reactants used in making
the condensation product is one mole of alkylphenol:0.1-10
moles of aliphatic amine:0.1-10 moles of aliphatic aldehyde. ~ `
A more preferred ratio is one mole o alkylphenol:0.5-3.0
moles of aliphatic amine:l.0-5.0 moles of aliphatic aldehyde. `~
The Mannich condensation product can be made by ~ ;
merely mixing the alkylphenol, aliphatic amine and aldehyde
in the proper ratio and heating the mixture to reaction
temperature. A suitable reaction temperature is about
50-200 C., and preferably 75-175 C. The condensation can
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be conducted without a solvent or a solvent may be
included. Suitable solvents are hydrocarbons having a ;~
boiling range of from about 70-20~ C. These include
both aliphatic and aromatic hydrocarbons such as heptanes J ` '
octanes, nonanes, benzene, toluene, xylene, mineral oils, `
and the like. Alcohols such as isopropanol canalso be
used. Optionally, the alkylphenol and arnine may be first
heated to reaction temperature and then the aldehyde
added at once, or over a period of time as the reaction ;~
proceeds. Likewise, the aldehyde and aliphatic amine
may be first mixed and heated and the alkylphenol added
to this mixture, or this mixture added to the alkylphenol. `~
The following examples illustrate the manner in
which the Mannich condensation product is prepared. ;;
EXAMPLE I ;~
To a reaction vessel equipped with a stirrer, ;~
c on denser and thermometer was added 363 parts of
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polybutene having an average molecular weight of 1100 and
94 parts of phenol. Over a period of 3 hours, 14.2
parts of a 48 percent BF3-etherate complex was added while
maintaining the reaction temperature between 50 and 60 C.
The reaction mixture was then stirred at 55-60 C. for an
additional 4.5 hours and then transferred to a second
reaction vessel containing 750 parts of water. The aqueous
phase was removed and the organic phase washed 4 times with
2S0 parts of water at 60 C. 7 removing the aqueous phase
after each wash. The organic product was then diluted with
about 200 parts of n-hexane and dried with anhydrous sodium
sulfate. The product was then filtered and the hexane and
other volatiles removed by vacuum distillation until the
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product remaining was at 75 C. at 0.3 mm. Hg. As a ;~
reaction product, there was obtained 368.9 parts of an
alkylphenol as a viscous amber-colored oil having an
average molecular weight of 810.
In a separate reaction vesseI was placed 267 ~ -
parts of the alkylphenol prepared above, 33.6 parts of
N,N-di-m~thyl-1,3-propanediamine and 330 parts of isopropanol.
While stirring, 15.8 parts of 95 percent paraformaldehyde `i~
was added. The reaction mixture was then refluxed for 1
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6.5 hours. Following this, the solvent and other volatiles `~
were distilled out to a reaction mass temperature of 115 C.
at about 15 mm. Hg. The reaction product was a viscous
amber-colored liquid.
EXAMPLE 2
In a reaction vessel was placed 933 grams of heptane,
495 grams of phenol and 3298 grams of polybutene (average l ~-
molecular weight 1000). An additional 315 grams of heptane
~ was added and the mixture stirred at 40-45 C. Over a
3 2 hour period, 147 grams of BF3 phenate was added while
stirring at 40-50 C. Stirring was continued for one hour
at 50 C. and then 972 grams of methanol was added. Following
this, 662 grams of aqueous c~mmonia was added and the mixture
heated to 60 C. Stirring was stopped and the mixture
I allowed to separate. The bottom aqueous layer was drained
l` off. The remaining product was washed with 972 grams of
,, methanol at 70 C. and again allowed to separate, following
;:J which the bottom layer was drained off.
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Temperature o~ the mixture was adjusted to 30 C.
and 365 grams of N,N-dimethyl-1,3-propanediamine and 171 grams
o~ paraformaldehyde was added. The mixture was stirr~d for
30 minutes at 35-40 C., following which the vessel was
evacuated to 100 mm. Hg. and volatiles distilled off up to
a liquid temperature of 150C. The residue was then diluted
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with 1313 grams of an aromatic solvent (Hysol 7D) giving a
c~ndensation product suitable for use in preparing the
sulfurized reaction products of this invention.
The sulfurized reaction product is prepared by
adding elemental sulfur to the Mannich condensation product
and heating the mixture to about 50-300 C. while stirring.
The condensation-product used in this reaction need not be ~'
purified. It can be subjected to the, sulfurization reaction
as it comes from the condensatlon reaction.
- Preferably, the sulfur is in the form of ~inely-
divided powder. The amount of sulfur added can vary over
a wide range. A useful range is about 1-20 parts by weight `~
of sulfur for each 100 parts of condensation product. Excess
sulfur can be used and any unreacted sulfur remaining ater `
sulfurization can be removed by such conventional methods
as centrifugation or filtration.
The ~ollowing example illustrates the manner by
which the s u 1 urized reaction products are made. ,
EX~LE 3
A solution was prepared containing 335 grams of the ~'
condensation product prepared in Example 2 and 165 grams of
SAE-7 mineral oil. To this was added 5 grams of sublimed
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sulfur and the mixture stirred at 120-125 C. ~or 10 hours.
The clear viscous product was cooled, resulting in an
effective lubricating oil dispersant hav:ing improved anti~
wear and anti-corrosion properties.
The above general procedure can readily be followed ;
to prepare a wide variety of reaction products of this
invention by substituting any of the condensation products
previously described and reacting them with various amounts
of sulfur at various temperatures.
Tests were carried out to demonstrate the improved
properties of the reaction products. In these tests a ~ ~ -
lubricating oil blend was prepared containing 0.5 weight `~
percent of a phenolic antioxidant, O.S weight percent of
tetrapropenyl succinic anhydride, 0.5 weight percent
I sulfurized synthetic sperm oil and 0.05 weight percent
I benzotriazole. ~o a portion of this blend was added
5 weight percent of the condensation product from ~
Example 2 and to a second portion was added 5 weight ~-
~ percent of the sulfurized reaction product of Example 3.
j A clean weighed copper-lead bearing was placed in each
I sample. The samples were heated to 325 F. and air bubbled
through them at a rate of 48 liters/hour ~or 96 hours. At ~-
I the end of this time the bearings were removed, cleaned and
I weighed. Bearing weight loss was used as a criteria of
~I the additive's anti-corrosion properties. The results
.~i obtained were as follows~
Additive Bearing Wt. Loss -
Example 2 416 mg.
Example 3 14 mg.
As these results show, the sulfurized reaction
~ product greatly reduced the corrosivity of the lubricating
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oil when compared to the same oil blend containing the
unsulfurized condensation product.
Further tests were carried out to demonstrate
the antiwear properties of the new additive. These
were 4 -ball wear tests in which the central ball of a
4 ball pyramid is rotated at 1800 r.p.m. under a 50 Kg ;~
load and the balls lubricated with an SAE-20 mineral oil
at 110 C. Criteria of effectiveness is the average
diameter of the scar which forms on the three stationary
balls. The smaller the scar diameter the more effective
the antiwear additive. One oil contained 5 weight percent ;~
ofthe additive of Example 2 and the other oil contained
S weight percent of the sulfurized additive of Example 3.
The results are shown in the following table.
Additive Scar Diameter (mm~
Example 2 2.75, 2.65
Example 3 2.02j 2.16
The above tests demonstrate that the dispersants
of the present invention possess both anticorrosion and
antiwear properties.
; The amount of reaction product added to the `
lubricating oil should be a small but effective amount
that is, it should be enough to impart the desired
discrepancy, antiwear and anticorrosion properties to
the oil. A useful range is from 0.3 to about 10 weight
percent. A more preferred range is from 1 to about 5
weight percent.
Other additives normally added to lubricating
oil can be included in the formulated oil. These include
metal sulfonates such as calcium alkarylsulfonates and
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magnesium alkarylsulfonates, zinc dialkyldithiophosphates J .' , :
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antioxidants such as 4,4'-methylenebis(2,6-di-tert-butyl- :
phenol), viscosity index improvers such as poly~lauryl-
methacrylates) polybutenes and ethylene-propylene
copolymers. Likewise, metal phenates such as barium or
zinc alkylphenates or sulfur-bridged metal phenates may
be included. Phosphosulfurized hydrocarbons and their . :
metal salts may be added such as the reaction product .:
of P2S5 with terpenes or polybutenes and their barium
salts. ~:~
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