CA1038539A - Lubricating oil dispersant - Google Patents
Lubricating oil dispersantInfo
- Publication number
- CA1038539A CA1038539A CA229,516A CA229516A CA1038539A CA 1038539 A CA1038539 A CA 1038539A CA 229516 A CA229516 A CA 229516A CA 1038539 A CA1038539 A CA 1038539A
- Authority
- CA
- Canada
- Prior art keywords
- product
- substituted phenol
- parts
- polyolefin
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Lubricants (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Dispersancy, wear and corrosion properties of lubricating oil are improved by addition of a product made by mixing at about 50-300° C. about 1-20 parts of sulfur with about 100 parts of the condensation product made by reacting a high molecular weight alkylphenol, formaldehyde and an aliphatic amine. Excess sulfur is preferably removed.
Dispersancy, wear and corrosion properties of lubricating oil are improved by addition of a product made by mixing at about 50-300° C. about 1-20 parts of sulfur with about 100 parts of the condensation product made by reacting a high molecular weight alkylphenol, formaldehyde and an aliphatic amine. Excess sulfur is preferably removed.
Description
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. '~
, 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.
: ,~
~' : ' ;~.
. ~
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
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. '~
, 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.
: ,~
~' : ' ;~.
. ~
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
- 2 -.
. . , 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.
: ~ ' '',,'`
. . , . . . . . . . . .~ . . . .. ~ . . . . ~
/ -~038539 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 : - 4 -, ' ':
1., . .,... ..... , , .. , .,., . ~ "
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 : . . .
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 , ~
, ' ."
" :~
~Q38S39 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 ~ ~,.... .
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.
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
. . , 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.
: ~ ' '',,'`
. . , . . . . . . . . .~ . . . .. ~ . . . . ~
/ -~038539 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 : - 4 -, ' ':
1., . .,... ..... , , .. , .,., . ~ "
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 : . . .
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 , ~
, ' ."
" :~
~Q38S39 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 ~ ~,.... .
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.
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.
;!
~,... ..
. .;
i! ~
'~ - 6 -.~
... ..
... .
., .
, .
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 ~ .~ .
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 .
7 ,~
~ 3~ ... .. . ", .
~ .
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 i l .,. , :
.-, ' - ~, ':
.~ .
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
;!
~,... ..
. .;
i! ~
'~ - 6 -.~
... ..
... .
., .
, .
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 ~ .~ .
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 .
7 ,~
~ 3~ ... .. . ", .
~ .
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 i l .,. , :
.-, ' - ~, ':
.~ .
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 ;'', .' ; ' ' .:
~Q3~539 magnesium alkarylsulfonates, zinc dialkyldithiophosphates J .' , :
': ~', ':; ' 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. ~:~
., .~ `
. .
:'' ' ~
"7 ~
''~' '"' .' ~.
;~'',; ~' . ' ~,':~ ' ':
: ~ , ' ' :
''' ~
,. ~,' ~, - 10- "~;''"' ' ' . . !
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 ;'', .' ; ' ' .:
~Q3~539 magnesium alkarylsulfonates, zinc dialkyldithiophosphates J .' , :
': ~', ':; ' 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. ~:~
., .~ `
. .
:'' ' ~
"7 ~
''~' '"' .' ~.
;~'',; ~' . ' ~,':~ ' ':
: ~ , ' ' :
''' ~
,. ~,' ~, - 10- "~;''"' ' ' . . !
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A product made by the process comprising heating to a temperature of about 50-300° C. a mixture of (1) from about 1-20 parts by weight of elemental sulfur and (2) about 100 parts by weight of a condensation product made by reacting about (a) one mole part of 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 from the group consisting of (i) aliphatic amine containing from 1 to about 20 carbon atoms and having at least one ?NH
group, (ii) piperidine and (iii) morpholine, and (c) about 0.1-10 mole parts of an aliphatic aldehyde containing from 1 to about 6 carbon atoms.
group, (ii) piperidine and (iii) morpholine, and (c) about 0.1-10 mole parts of an aliphatic aldehyde containing from 1 to about 6 carbon atoms.
2. A product of Claim 1 wherein said alkylphenol is a polyolefin-substituted phenol and said aldehyde is formaldehyde.
3. A product of Claim 2 wherein said polyolefin-substituted phenol is a polypropylene-substituted phenol.
4. A product of Claim 2 wherein said polyolefin-substituted phenol is a polybutene-substituted phenol.
5. A product of Claim 2 wherein said aliphatic amine is an ethylene polyamine having the formula:
H2N ? CH2-CH2NH ?x H
wherein x is an integer from 1 to about 6 and mixtures thereof.
H2N ? CH2-CH2NH ?x H
wherein x is an integer from 1 to about 6 and mixtures thereof.
6. A product of Claim 5 wherein said polyolefin-substituted phenol is a polypropylene-substituted phenol.
7. A product of Claim 5 wherein said polyolefin-substituted phenol is a polybutene-substituted phenol.
8. A product of Claim 2 wherein said aliphatic amine is an N,N-dialkyl-alkanediamine.
9. A product of Claim 8 wherein said polyolefin-substituted phenol is a polybutene-substituted phenol.
10. A product of Claim 9 wherein said alkanediamine is N,N-dimethyl-1,3-propanediamine.
11. A product of Claim 10 wherein said polybutene substituent has an average molecular weight of about 750-1500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA229,516A CA1038539A (en) | 1975-06-17 | 1975-06-17 | Lubricating oil dispersant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA229,516A CA1038539A (en) | 1975-06-17 | 1975-06-17 | Lubricating oil dispersant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1038539A true CA1038539A (en) | 1978-09-12 |
Family
ID=4103363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA229,516A Expired CA1038539A (en) | 1975-06-17 | 1975-06-17 | Lubricating oil dispersant |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1038539A (en) |
-
1975
- 1975-06-17 CA CA229,516A patent/CA1038539A/en not_active Expired
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3904595A (en) | Lubricating oil dispersant | |
| US3957746A (en) | Phospho-sulfurized phenolic aldehyde amine alkylene oxide condensation product | |
| US4058468A (en) | Lubricant composition | |
| US3725277A (en) | Lubricant compositions | |
| US3036003A (en) | Lubricating oil composition | |
| US3322670A (en) | Detergent-dispersant lubricant additive having anti-rust and anti-wear properties | |
| US4176074A (en) | Molybdenum complexes of ashless oxazoline dispersants as friction reducing antiwear additives for lubricating oils | |
| CA2089712C (en) | Mannich reaction product and process for producing the same and use of the product | |
| US4965004A (en) | Process for a borated detergent additive | |
| GB1583361A (en) | Mannich base composition | |
| US4242212A (en) | Mannich additives modified by ditertiary alkyl phenol | |
| US5302304A (en) | Silver protective lubricant composition | |
| EP0136820B1 (en) | Copper complexes of oxazolines and lactone oxazolines as lubricating oil additives | |
| JPH0138840B2 (en) | ||
| US4483775A (en) | Lubricating oil compositions containing overbased calcium sulfonates | |
| CA1038851A (en) | Dispersant-detergent libricant and fuel additives | |
| US4248725A (en) | Dispersants having antioxidant activity and lubricating compositions containing them | |
| CA1192552A (en) | Method for preparing nitrogen- and oxygen-containing compositions useful as lubricant and fuel additives | |
| WO2002059240A2 (en) | Hydroxy aromatic mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions | |
| US3764536A (en) | Overbased calcium salts of alkenylsuccinimide | |
| US5160649A (en) | Multifunctional ashless detergent additives for fuels and lubricants | |
| CA1038539A (en) | Lubricating oil dispersant | |
| US3761414A (en) | Sulfurized calcium alkylphenolate lubricants | |
| US4131553A (en) | Alkylbenzene sulfonic acid modified mannich reaction products from oxidized polymers | |
| CA1339530C (en) | Polyolefinic succinimide polyamine alkyl acetoacetate adduct dispersants |