|Publication number||US2459112 A|
|Publication date||Jan 11, 1949|
|Filing date||Jul 6, 1945|
|Priority date||Jul 6, 1945|
|Publication number||US 2459112 A, US 2459112A, US-A-2459112, US2459112 A, US2459112A|
|Inventors||Edward A Oberright|
|Original Assignee||Socony Vacuum Oil Co Inc|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (4), Referenced by (86), Classifications (18)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Prams Jan. 11, 1949 MINERAL OIL COMPOSITION Edward A. Oberright, Woodbury, N. J., assignor to Sooony-Vaeuum Oil Company, Incorporated, a corporation of New York No Drawing. Application July 6, 1945, Serial No. 603,587
This invention has to do in a general way with mineral oil compositions and is more particularly related to compositions comprised of mineral oil and a minor proportion of an added ingredient which will improve the oil in one or more important respects.
It is well known to those familiar with the art that mineral oil fractions refined for their various uses are in and of themselves usually deficient in one or more respects so that their practical utility is limited even in the particular field for which. they have been refined. For example, mineral oil fractions refined for use as lubricants have a tendency to oxidize under conditions of use, with the formation of sludge or acidic oxidation products; also, the lighter fractions such as gasoline and kerosene tend to oxidize with the formation of color bodies, gum, etc. In order to prevent the formation of these products and thereby extend the useful life of the oil fraction, it is common practice to blend with such oil fraction an additive ingredient which will inhibit oxidation, such ingredients being known to the trade as oxidation inhibitors, antioxidants, sludge inhibi-- tors, gum inhibitors, etc.
It is also the, practice to add other ingredients to mineral oil fractions for the purpose of improving oiliness" characteristics and the wearreducing action of such mineral oils when they are used as lubricants, particularly when the oils are used for the purpose of lubricating metal surfaces which are engaged under extremely high pressures and at high rubbing speeds.
Various other ingredients have been developed for the purpose of depressing the pour point of mineral oil fractions which have been refined for use as lubricants. Most refining treatments provide oils containing a small amount of wax which, without the added ingredient, would tend to crystallize at temperatures which render the oil impracticable for use under low temperature conditions. Additive agents have also been developed for improving the viscosity index of lubricating oil fractions. In the case of internal combustion engines, particularly those operating with high 'cylinder pressures, there is a decided tendency for the ordinary lubricating oil fractions to form carbonaceous deposits which cause the piston rings to become stuck in their slots and which fill the slots in the 01] ring or rings, thus ma- 18 Claims. (Cl. 252--5l.5)
terially reducing the eillciency of the engine: 51ngredients havebeen developed which, when added to the oil, will reduce this natural tendency of the oil to form deposits which interfere with the function of thepiston rings. It has also been discovered that certain types of recently-developed hard metal alloys, such as cadmium-silver alloy bearings, are attacked by ingredients in certain types of oils, particularly oils of high viscosity index obtained by various methods of solvent-refining. This corrosive action on such alloys has led to the development of corrosion-inhibitors which may be used in solvent-refined oils to protect such bearing metals against this corrosive action.
In the lighter mineral oil fractions. such as those used for fuel purposes, particularly in internal combustion engines, it has been found able solvent.
that the combustion characteristics of the fuel may be controlled and improved by adding minor proportions of various improving agents thereto.
The various ingredients which have been developed for .use in mineral oil fractions to improve such fractions in the several characteristics enumerated above are largely specific to their particular applications. Therefore, it has been the practice to add a separateingredient for each of the improvements which is to be effected.
The present invention is predicated upon the discovery of a group or class of oil-soluble reaction products or compounds which, when added to mineral oil fractions in minor proportions, will improve the oil fractions in several respects.
The novel addition agents contemplated by this invention as multi-functional improvers for mineral oils are the condensation products of an aldehyde, a polyamine in which each amino group is characterized by the presence of at least one hydrogen atom, and a hydroxyaromatic compound. Preferred reaction products are those obtained by condensing about one molar equivalent of an aldehyde with at least one-quarter molar equivalent of a polyamine of the aforementioned character and a molar equivalent of a hydroxyaromatic compound. The condensation is preferably carried out in the presence of a suit- Aldehydes contemplated by the present invention are the aliphatic aldehydes, typified byv dehyde, tend aldol (fi-hydroxy butyraldehyde);
aromatic aldehydes, representative of which is benzaldehyde; heterocycllc aidehydes, such as iuriural; etc. The aldehyde may contain a substituent group such as hydroxyl, halogen, nitro and the like; in short, any substituent which does not take a major part in the reaction. Preier are the aliphatic homologs, ethylene diamine;
propylene diamine, polyalkene polyamines (e. g., diethylene triamine, triethylene tetramine); the aromatic homologs, mand p-phenylene diamine, diamino naphthalenes, etc. Of this class of amines, preference is given to the diamines in which two primary amino groups are attached to adjacent carbon atoms, and particular preference is accorded ethylene diamine.
Representative hydroxyarornatic compounds contemplated by the present invention are phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxydiphenyl, benzylphenol, phenylethylphencl, phenol resins, methylhydroxydiphenyl, guiacol, alpha and beta naphthol, alpha and beta methylnaphthol, tolylnaphthol, xylylnaphthol, benzylnaphthol, anthranol, phenylmethylnaphthol, phenanthrol, monomethyl ether of catechol, phenoxyphenol, chlorphenol, and the like. Preference in general is to the monohydroxy phenols otherwise unsubstituted, particular preference being given to phenol and alpha and beta naphthol.
As indicated hereinabove, the hydroxyaromatic compound may contain one or more alkyl substituents such as short-chain groups, typified by methyl, ethyl, amyl, etc.; or long-chain, relatively-high-molocular-weight h y d r o c a r b o 11 groups having at least twenty carbon atoms, typified by alkyl groups derived from petroleum wax, which is a predominantly straight-chain aliphatic hydrocarbon of at least twenty carbon atoms. It will be obvious to those skilled in the art that the maximum number of alkyl groups is limited by the number of valences on the aromatic nucleus available for substitution. Naturally, the maximum number of such groups which can be attached to a single aromatic nucleus will vary as the nucleus is monoor polycyclic and as the nucleus is otherwise substituted, with such groups as carboxy, nitro, amino, halogen and the like.
The present application has been purposely directed to condensation products of the aforesaid reactants for, as yet, the theory of reaction is not fully understood. Some evidence is availableior example, quantitative analysis of the reaction product-to point to the presence oi! a major quantity of one compound. For instance, when typical reactants, such as an alkyl-substituted phenol, formaldehyde and ethylene diamine, are reacted as hereinafter described, analysis indicates that the predominant product is:
no on n n n n n n i t i t i i t t wherein R is an alkyl group.
Probably also present in the condensation product are compounds of the following type:
Q5 m-c-m and R .10 g E; H: H H in The foregoing is for illustrative purposes only and is not to be construed as limiting the present invention to a theory of reaction because the present invention is directed primarily to condensation products obtained by inter-reaction oi the reactants described herein as multifunctional improving agents for lubricating oils and the like.
In preparing the condensation products contemplated herein, the reactants may be added to each other in any order. A typical procedure involves adding the aldehyde to an alcohol solution of the hydroxyaromatic compound and the amine. The reaction may also be carried out in the presence of other diluents or solvents such, for example, as tetrachlorethane, chlorbenzene, mineral oil, etc. In'the event that mineral oil is used as a diluent, the mineral oil may be retained, rather than separated from the reaction product, thereby providing a mineral oil concentrate.
The reaction temperature may be varied considerably, depending upon the time of reaction, the specific reactants used, etc. For example, the reaction can be carried out at room temperature over a relatively long period of time or at the reflux temperature of the solvent over a comparativeiy short period. By way of illustration, the reactants, in quantities such as shown in the following examples, may be thoroughly mixed at room temperature for several hours and the reaction completed at the reflux temperature of the solvent for an additional period of several hours.
The reaction product may be water washed to assure complete removal of any unreacted amine and this is recommended when the amine is high boiling. When an alcohol is used as a diluent in the reation, it is distilled from the reaction mixture, thereby also removing any unreacted amine and water of reaction or water added with the reactants (Formalin, tor example, is generally used in a 37% aqueous solution).
As stated above, the general procedure for preparing the contemplated condensation products involves the interreaction of a hydroxyaromatic compound, angaliphatic aldehyde, and a polyamine wherein the amino groups have at least one free hydrogen.
A typical, and also preferred, alkyl-substituted hydroxyaromatic compound which may be used is a wax-substituted phenol, wax-phenol." The term wax" as used herein designates petroleum wax or aliphatic hydrocarbons or hydrocarbon groups of the type which characterize petroleum wax. These so-called wax substituen'ts may be obtained by alkylation of the phenol or hydroxy-aromatic' hydrocarbon with a relativelyhigh-molecular weight aliphatic hydrocarbon or mixture of such hydrocarbons (such as petroleum wax) by any suitable alkylationprocedure such, for example, as by a Friedel-Crafts condensation of chlorinated petroleum wax with phenol.
Details of a preferred procedure for making the condensation products of this invention I where the aforesaid wax-phenol is employed as the alkyl-substituted hydroxyaromatic compound may be obtained from the following examples:
EXAMPLE I- A. Alleviation of phenol A parafiln wax melting at approximately 120 F. and predominantly comprised of compounds having at least twenty carbon atoms in their molecules is melted and heated to about 200 F.,
.after which chlorine is ,bubbled therethrough until the wax has absorbed about 16 percent of chlorine, such product having an average composition between a monochlor wax and a dichlor wax. PreferabIy the chlorination is continued until about one-sixth the weight of the chlorwax formed is chlorine. A quantity of chlorwax thus obtained, containing two atomic proportions of chlorine-is heated to a temperature washing. but it is preferable to treat the waterwashed product with superheated steam, thereby insuring complete removal of the unreacted material and accomplishing the drying of the product in the same operation.
A wax-substituted phenol prepared according to the above procedure in which a quantity of chlor-wax containing two atomic proportions of chlorine and having a chlorine content of 16 percent is reacted with 1 mol of phenol will be hereinafter designated as "wax-phenol (246)."
- B. Formation of final product after heated for two hours atreilux, about 110 C.
'Eighty grams of a mineral oil (S. U. V. of 65 seconds 210 F.) were then added to the reaction mixture, and butyl alcohol was distilled therefrom, the maximum distillation temperature being 190 .C. at 10 mms. pressure. The oil blend (2:5) of the reaction product thus obtained contained 2.3 percent nitrogen. This material is identified hereinafter as Product One."
varying from Just above its melting point to not over 150 F., and one mol of phenol (CeHaOH) is admixed therewith. The mixture is heated to about 150 F., and a quantity of anhydrous aluminum chloride corresponding to about 3 percent of the weight of chlor-wax in the mixture is slowly added with active stirring. The rate of addition of the aluminum chloride should be sufficiently slow to avoid violent foaming, and
- during such addition the temperature should be held at about 150 F. After the aluminum chloride has been added, the temperature of the mixture may be increased slowly over a period of from 15 to 25 minutes to a temperature of about 250 F. and then should be more slowlyincreased to about 350 F. To control the evolution of HCl gas the temperature of the mixture is preferably raised from 250 F. to 350 F., at a rate of approximately one degree per minute, the whole heating operation occupying approximately two hours from the time of adding the aluminum chloride. If the emission of HCl gas has not ceased when the final temperature is reached, the mixture may be held at 350 F. for a short time to allow completion of the reaction. However, to avoid possible cracking of the wax, the mixture should not be heated appreciably above 350 F., nor should it be held at that temperature for any extended length of time.
It is important that all unreacted or nonalkylated hydroxyaromatic material (phenol) remaining after the alkylation reaction be removed.
such removal can be effected generallyby water- Exam II- A. Alkylation of phenol A paraffin wax melting at approximately 120 F. and predominantly comprised of compounds having at least twenty carbon atoms in their molecules was melted and heated to about 200 F., after which chlorine was bubbled therethrough according to the procedure followed in Example I, section A, except that the chlorination was continued until the wax had absorbed about 16 percentchlorine. A quantity of chlor-wax thus obtained, containing 3 atomic proportions of chlorine, was heated to a temperature varying from just above its melting point to not over F., and 1 mol of phenol (CcHsOI-I) was admixed therewith. The mixture was then subjected to the procedure followed in Example I to give a wax-substituted phenol which will be hereinafter designated as wax-phenol (3-16) B. Final product Seven hundred grams of wax-phenol (3-16), prepared according to the foregoing procedure, and 61.2'grams of a 60 percent solution of ethylene diamine in water were dissolved in butyl alcohol. To the alcohol solution were added dropwise 82.8 grams of Formalin. After stirring at room temperature (about 25 C.) for two hours, the reaction mixture was heated at reflux temperature (110 C.) for 6 hours. The reaction mixture was washed with four separate portions of water, the last wash water having a pH of 7. Butyl alcohol was removed from the reaction mixture by distilling the same to a maximum temperature of C. at 10 mms. pressure. The final product-Product TWO-is a wax-like substance having a nitrogen content of 1.73 percent.
'prepared as described in Example II, section A,
15.8 grams of ortho-phenylene diamine. 100
grams of mineral oil (S. U. V. of 65 seconds at 210 F.) and 150 cc. of butanol were heated to about 50 C. to form aclear solution. Aldoi (fihydroxybutyraldehyde) 25.6 grams.- was added to the alcohol solution thus obtained over a period of minutes. After heating the resulting reaction mixture to the reflux temperature (110 C.) for eight hours, the reaction mixture was waterwashed until the wash water was neutral. Butyl alcohol was then removed by distilling the waterwashed reaction mixture to a maximum temperature of 190 C. at mms pressure. The mineral oil blend (1:2) of the reaction product contained 1.6 percent nitrogen, and is identified hereinafter as Product Three.
Other typical examples in which the hydroxyaromatic compound contains a diflerent alkyl substituent, or no such substituent,are provided below.
Seventy-eight grams of diamyl phenol, 2'?
grams of Formalin and 29 grams of a 69 percent solution of ethylene diamlne in water were dissolved in a mixture of butyl and methyl alcohols.
The alcoholic solution thus obtained was stirred at about C. for 4 hours and then allowed to stand for 48 hours. Thereafter it was stirred again at 25 C. for 5 hours. After one waterwash, the alcohols and any unreacted dlamyl phenol were removed from the reaction mixture by distilling the same to 230 C. at 10 ms. pressure. The product-Product Four-thus obtained is an oil-soluble, low melting resinous substance having a nitrogen content of 5.7 percent.
EXAMPLE V Thirty grams of a 95 percent solution of ethylene diamine in water were dissolved in butyl alcohol, and 45 grams of Formalin were added thereto while cooling the reaction vessel with an ice bath. Butyl alcohol was evaporated from the reaction mixture so obtained until white crystals formed therein. After cooling the reaction mixture, the crystals were filtered therefrom. The crystals were recrystallized from butyl alcohol.
They are soluble in ether, ethyl alcohol, waterand mineral oil, but insoluble in petroleum ether. They have a melting point of 163-165 C. and a nitrogen content of 30.96 percent.
Two grams of the crystals obtained above were dissolved in 95 percent ethyl alcohol; three grams As stated herelnbefore, .the reaction products contemplated by this invention and illustrated by the above examples, when added to lubricating oils in minor proportions, have been found to improve these oils in several important respects. This phenomenon is demonstrated by the following tables, which give the results of the various tests conducted to determine the effectiveness of these reaction products as addition agents for lubricating oils. The percent of material added to the oil in the following tables is the percent of concentrated material and does not include the oil in which the product was made.
Form Form Dsraassrou Tests were conducted in the conventional manner to determine the A. S. T. M. pour points of blends of these reaction products with a Mid- Continent solvent-refined oil of Saybolt Universal viscosity. of 67 seconds at 210 F. as compared with the pour point of the blank oil. The results given in Table I below demonstrate the eflfectlveness of the reaction products contemplated herein as pour point depressants.
CORROSION Tss'r In this test the reaction product was blended with a Pennsylvania solvent-refined oil of Saybolt Universal viscosity of 53 seconds at 210 F., and a section of a bearing containing a cadmium-silver alloy surface and weighing about 6 grams was added to this blend. The oil was heated to 175 C. for 22 hours while a stream of air was bubbled against the surface of the hearing. The loss in weight of the bearing during this treatment measured the amount of corrosion that had taken place. A sample of the straight oil was subjected to the same test at the same time, and the difference between the losses in weight of the two bearing sections demonstrated conclusively the effectiveness of the reaction products contemplated herein as corrosion-inhibitors.
SOCONY-VACUUM TURBINE TEST Twenty-five cc. samples of a furfural-reflned Rodessa crude of Saybolt Universal viscosity of 150 seconds at F. and of blends of thlssame oil and typical reaction products were subjected to the following test to determine the effectiveness of the reaction products contemplated by this invention as inhibitors for turbine oils: To each sample were added 1 gram of iron granules and 16- 24 inches of 18 gauge copper wire. The samples 5 liters of air per hour bubbling therethroush.
were then heated to a temperature or 200? P. with Two cc. of distilled'wate'r were addedeach dam; The results of the tests which were made-tor color I and acidity or neutralization number of sludge formed after certain time-intervals set forth in Table m below.
e imen f a cold was steel disc (1 in in a. V4 inch thick) with 1 highly polished concave" surface facing upward wasplaced in a' 50ml. class beaker. A 25 ml. sample of the oil or oil -blend was introduced into the beaker, which was held in a constant temperature bath at 90 F.,-for 30 minutes. One-tenth (0.1) ml. of distilled water 1 i I w 10 The improved properties obtained and the degree of improvement efl'ected maybe varied with the aldehyde, polyamine and hydroxyaromatic "compounds.- For example, when. the hydroxyaromatic nucleus contains one or more of the preferred "waxi substituenta'thev reaction product obtained therewith is'characterized by pour depressant action and an extremely high order of rust inhibiting properties.
" H The amount of improving agent used varies withthe mineral oil or lubricating oil fraction with which it'is blended and. with the properties desired in the final'oil composition. These re- -am0unts of from about 0.00I to about 10 percent, butamounts of from about 0.1percent to about provement. 1
described certain preferred procedures which may befollowed in the preparation of the novel reaction products contemplated herein as multifunctional addition agents for mineral oils and 'was carefully added so that 1 drop of water rested on the concave surface of the steel disc. The steel disc was then observed for the first appearance of rust and the time recorded. The oil used was an acid-treated oil or 140-155 seconds 3. my. at 100 1'. The results of these tests are shown in Table IV following:
' To demonstrate the effectiveness of the reaction products under actual operating conditions of an automotive engine. unblended oils and improved oils, containing the reaction products, were subiected to the Lauson engine test. The tests were carried out in a'single-cylinder Lauson engine operated continuously over a time interval 01-16 hours with'the cooling medium held at a temperature of about 212 F., and the oil temperature held at about-280 F. The engine was operated at a speed of about 1830 R. P. M. At the end of each test thejoil was tested for acidity (N. N.)
. and viscosity. The base oil used here is a solvent refined oil having an S. U. V. o! 44 seconds at 210 F. 1 V
Table V Addition Agent 25%, 5: 1;: N.
1 None 50.1 5.5 Product One K 44.9 0.5 None 50.7 40 Product Ono 45.7 i 1. 1
It will be apparent from the foregoing test data that'the reaction products of this invention are eiiective nofl only to inhibit corrosion and the various eifects of oxidation upon mineral oils such as formation of rust; sludge. color bodiesand other undesirable products,'but also to depress the pour point.
have indicated representative reactants for in their preparation, such procedures and reactants are merely illustrative and the invention is not to be considered aslimited thereto orthereby but includes within its scope'such changes and modifications as fairly come within the spirit'oi' the appended claims. Iclaimf 1. An improved mineral oil containinga minor action products may be added to mineral oil in 3 percent generally provide satisfactory 1111-.
It is to be understood that although I have proportion, sufllcient to depress the pour point and improve the oxidation stability ofsaid oil, of a reaction product obtained by reaction, at a temperature within the range of from about-25 C. to about 110 0., of analdehyde, a hydroxyaromatic compound and each aminogroup has at least on hydrogen atom: the proportions of reactants, on the basis of one moi of aldeh'yde'being about onemol of hydroxyaromatic compound and at least about one-fourth mol of polyamine.
2. An improved mineral 011 containing a minor proportiomfrom about 0.001 percent .to about 10 percent, of a reaction product obtained by reaction, at a temperature within the range of from about 25 C. to about 410 C., of an aldehyde, a 'hydroiryaromatic compound and a-polyamine in whicheach amino group has at least one hydrogen atomythe proportions of reactants,.on the basis of one mol of aldehyde being about one mol one-fourth mol of polyamlne.
of hydroxyaromatic compound and at 3. An improved mineral ollcontaining ,a minor polyamine in which least about proportion,-suflicient to depress the pour point and improve the oxidation stability of said on,
of a reaction-product obtained by reaction, at a temperature within the range or from about 25 C. to about 0.. of an aliphatic'aldehyde, a
hydroxyaromatic compound-and a polyamine in which each amino group has at least one hydro I gen atom: the proportions oi reactants. on the basis of one mol ot aliphatic aldehyda being .05.
about mol of hydro ryaromatic compound and at least Y about one fourth molof, .polyarnine.
4. .An improved mincraloil-contfaininga minor proportion, sumcient to idepress the-pourpoint and improve [the oxidationstability of said 011, of areaction product. obtained by reaction. at a temperature. within the lrangeijorirom about 25 PC. to about 110 Q., of'formaidehyde a hydroxyaromatic compound and a polyamine in which each amino group has at least one hydrogen atom; the proportions of reactants, on the basis mol of ethylene dlamine.
one-fourth molbi polyalnine.
5. An improved mineral oil containing a minor proportion, suiiicient to depress the poor point and improve the oxidation stability of said oil. oi a reaction product obtained by reaction. at a temperature within the range oi irom about 25 C. to about 110 C., o! an aldehyde, a hydroxy-- aromatic compound and an aliphatic polyamine in which each amino groupha's at least one hydrogen atom; the proportions at reactants. on the basis oi one mol oi aldehyde. being about one mol hydroayaromatic compound and at least about one-fourth moi oi aliphaticpoiyamine.
6. An improved mineral oil containing a minor proportion, suihcient to depress the poor point and improve the oxidation stability ,0! said oil.
' oi a reaction product obtained by reaction, at a ture within the range oi irom about 25'? to about 110, oi an aldehyde, a tic compound and an aliphatic polyamine having two primary amino groups attached to'adiacent carbon atoms: the us of reactants. on the basis of one moi oi aldehyde, being about one mol oi hydroxyaromatic compound and at least about one-iourth moi oi polyamine.
'I. An improvedmineral oil proportion, suiiicientto depress the pour point and improve the oxidation stability of said oil. of a reaction product obtained by reaction. at'a temperature within the range of irom about 25 C. to about-110 (2., of an aldehyde, a hydroxyaromatic compound and ethylene diamine; the proportions of reactants. on the basis of one mol of aldehyde, being about one mol of hydrorlraromatic compound and at least about one-fourth 8.:An improved mineral oil containing a minor proportion, sui'ilcient to depress the pour point and improve the oxidation stability oi said oil. of a reaction product obtained by reaction. at a temperature within the range of from about 25 C. to about 110 6., of an aldehyde. an alkylsubstituted hydroxyaromatic compound ,wherein the alkyl substituent contains at least twenty carbon atoms and a polyamine in which each amino group has at least one hydrogen atom; the proportions of reactants, on the basis of one mol of aldehyde, being about one mol of alkyl-substituted hydroxyaromatic compound and at least about one-fourth mol of polyamine.
V 9. An improved mineral oil containing a minor proportion, suiiicient to depress the pour point and improve the oxidation stability or said oil, of a reaction product obtained by reaction, at a temperature within the range oi from about 25 C. to about 110 0.. of an aldehyde, a wax substituted hydroxyaromatic compound and a polyamine in which each amino group has at least onehydro gen atom; the proportions of reactants, on the basis of one mol of aldehyde. being about one mol oi wax-substituted hydroxyaromatic compound and at least about one-fourth. mol of polyamine.
10. an improved mineral oil containing a minor proportion, suilicient to depress the pour point and improve the oxidation stability of said oil. oi a reaction product obtained by reaction, at a temperature within the range of from about 25 0.11:0 about 110 C., of an aldehyde, a wax phenol and a'polyamine in which each amino group has at least one hydrogen atom; the .proportions oi reactants. on the basis oi one mol of aldehyde.
being about one mol oL-wax phenol and at least 4 about one-fourth mol of polyamine.
aesa'ua a containingaminor- 11.. An proportion, suiiicient to depress the poor point and improve the oxidationstability or said oil. of a reaction product obtained by reaction, at a s temperature within the range of from about 25 C. to about 110' (2.. 01' an aldehyde. diamyl'phenol andapolyamineinwhicheachaminogrouphas at least one hydrosenatom; the proportions oi reactants, on the basis oi one mol oi aldehyde. being about one mol at diamyl phenol andat least about one-fourth mol oi polyamine.
12. An improved mineral oil=containing a minor propottlm, sumcient to 1109188! the pour point I and improvethe ouidation stability 0! said oil, s of a reaction ploduct obtained by reaction, at a temperature within the range 01! from about 35 C. toabout 110' 0., oian aldehyde, fi-naphthol and apoiyamine in which each amino group has at least one hydrogen atom; the proportions of re- 5 actants, on thebasisoi one mol oi aldehyde, being about one mol of B-naphthol and at least about .one-iolirth mol of poll's-mine. V r 13.- An improved mineral oil containing a minor proportion, suiiicient to-depress the pour point a and improve the oxidation stability of said oil, of a condensation product obtainedby reaction. at a temperature within the range 01 from about 8.. to about 110 0.. of formaldehyde. wax-phenol and ethylene diamine; the proportions oi reactso ants. on the basis of one mol oi formaldehyde. being about one mol of wax phenol and at least about one-fourth mol of ethylene diamine.
14. An improved mineral oil containing a minor proportion, suflicient to depress the pour point as and improve the oxidation stability of said oil.
of a condensation product obtained by reaction, at a temperature within the range of. from about 25 C. to about 110 C., oi iormaldehyde. diamyl phenol and ethylene diamine; the proportions oi 4c reactants. on the basis of one mol of formaldehyde, being about one mol of diamyl phenol and at least about one-fourth mol oi ethylene diamine. 15. An improved mineral -oil containing aminor proportion, suillclent to depress the pour point 4.1 and improve the oxidation stability of said oi].
oi a condensation product obtained by reaction. at atemperature within the range of from about C. to about-110 C., of p-naphthol and a product obtained by reaction ofiormaldehyde and ethylene diamine: the proportions oi reactants. on the basis of one mol of formaldehyde, being at least about one-fourth moi of ethylene diamine and about'one mol oi p-naphthol.
16. A mineral oil concentrate containing upwards oi 10% oi arreaction product obtainedby reaction. at a temperature within the range of irom'about 25 C. to about 110 0., of an aldehyde. a hydroxyaromatic compound and a polyamine in which eachramino group has at least one hydroso gen atom; the proportions oiireactants, on the basis of one mol of aldehyde, being about one mol of hydroxyaromatic compound and at least about one-fourth mol of polyamine.
EDWARD A. OBERRIGHT.
In ;4' one! 058 CITED UNITED STATES PA'I'ENTS Number Name Date 2,334,594 Zimmer Nov. 16, 1948 2,348,839 Mikesha --a May 9, 1944 2,363,192 Sargent -a July 11, 1944 I '75 2,368,134 MoCleary Non-21, 1944 improvedmineraioileontainingaminor
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2334594 *||Jan 29, 1941||Nov 16, 1943||Standard Oil Dev Co||Lubricant composition|
|US2348639 *||Sep 30, 1941||May 9, 1944||Jolly W O'brien||Identifying substance|
|US2353192 *||Jan 21, 1942||Jul 11, 1944||Socony Vacuum Oil Co Inc||Stabilized fuel oil composition and method thereof|
|US2363134 *||Apr 26, 1941||Nov 21, 1944||Texas Co||Lubricating oil|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2962442 *||Jan 3, 1957||Nov 29, 1960||Socony Mobil Oil Co Inc||Preparation of aldehyde-polyamine-hydroxyaromatic compound condensates and hydrocarbon fractions containing the same|
|US3036003 *||Aug 7, 1957||May 22, 1962||Sinclair Research Inc||Lubricating oil composition|
|US3149933 *||Aug 1, 1961||Sep 22, 1964||Bayer Ag||Process for stabilizing liquid fuels|
|US3269810 *||Sep 19, 1963||Aug 30, 1966||Nalco Chemical Co||Antioxidants for cracked petroleum distillates, especially gasoline|
|US3288713 *||Nov 14, 1963||Nov 29, 1966||Sinclair Research Inc||Synthetic ester lubricants containing antioxidants|
|US3368972 *||Jan 6, 1965||Feb 13, 1968||Mobil Oil Corp||High molecular weight mannich bases as engine oil additives|
|US3413347 *||Jan 26, 1966||Nov 26, 1968||Ethyl Corp||Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines|
|US3649229 *||Dec 17, 1969||Mar 14, 1972||Mobil Oil Corp||Liquid hydrocarbon fuels containing high molecular weight mannich bases|
|US4117011 *||May 6, 1974||Sep 26, 1978||Ethyl Corporation||Additives|
|US4454059 *||Apr 16, 1981||Jun 12, 1984||The Lubrizol Corporation||Nitrogenous dispersants, lubricants and concentrates containing said nitrogenous dispersants|
|US5183940 *||May 11, 1992||Feb 2, 1993||Imperial Chemical Industries Plc||Poly-(n-[2-hydroxybenzyl])-1,2-diaminoethanes|
|US5308595 *||Nov 13, 1992||May 3, 1994||Imperial Chemical Industries Plc||Process for the extraction of gallium|
|US5498809 *||May 22, 1995||Mar 12, 1996||Exxon Chemical Patents Inc.||Polymers derived from ethylene and 1-butene for use in the preparation of lubricant dispersant additives|
|US5554310 *||Jun 9, 1994||Sep 10, 1996||Exxon Chemical Patents Inc.||Trisubstituted unsaturated polymers|
|US5576108 *||Sep 9, 1994||Nov 19, 1996||Hoechst Aktiengesellschaft||Curing component for epoxy resins|
|US5578685 *||Jun 2, 1995||Nov 26, 1996||Hoechst Aktiengesellschaft||Curing component for epoxy resins comprising Mannich base from alkylated polyhydroxy aromatic|
|US5663130 *||Mar 11, 1996||Sep 2, 1997||Exxon Chemical Patents Inc||Polymers derived from ethylene and 1-butene for use in the preparation of lubricant dispersant additives|
|US5814111 *||Aug 6, 1996||Sep 29, 1998||Shell Oil Company||Gasoline compositions|
|US6030930 *||May 14, 1997||Feb 29, 2000||Exxon Chemical Patents Inc||Polymers derived from ethylene and 1-butene for use in the preparation of lubricant disperant additives|
|US6627584||Jan 28, 2002||Sep 30, 2003||Ethyl Corporation||Automatic transmission fluid additive comprising reaction product of hydrocarbyl acrylates and dihydrocarbyldithiophosphoric acids|
|US6855674||Dec 2, 2002||Feb 15, 2005||Infineum International Ltd.||Hydroxy aromatic Mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions|
|US7214649||Dec 31, 2003||May 8, 2007||Afton Chemical Corporation||Hydrocarbyl dispersants including pendant polar functional groups|
|US7645728||Jan 12, 2010||Afton Chemical Corporation||Lubricant and fuel additives derived from treated amines|
|US7833953||Nov 16, 2010||Afton Chemical Corporation||Lubricant composition|
|US7879775||Jul 14, 2006||Feb 1, 2011||Afton Chemical Corporation||Lubricant compositions|
|US7888299||Jan 13, 2004||Feb 15, 2011||Afton Chemical Japan Corp.||Extended drain, thermally stable, gear oil formulations|
|US7902133||Mar 8, 2011||Afton Chemical Corporation||Lubricant composition|
|US7947636||Feb 27, 2004||May 24, 2011||Afton Chemical Corporation||Power transmission fluids|
|US8377336||Feb 19, 2013||Basf Se||Use of polynuclear phenolic compounds as stabilisers|
|US8409474||Feb 21, 2007||Apr 2, 2013||Basf Se||Use of polynuclear phenolic compounds as stabilisers|
|US8546311||Mar 10, 2009||Oct 1, 2013||Volkswagen Aktiengesellsschaft||Method for lubricating a clutch-only automatic transmission component requiring lubrication|
|US8557752||Mar 22, 2006||Oct 15, 2013||Afton Chemical Corporation||Lubricating compositions|
|US8703669||Feb 17, 2009||Apr 22, 2014||Afton Chemical Corporation||Ultra-low sulfur clutch-only transmission fluids|
|US9267093||May 21, 2010||Feb 23, 2016||Afton Chemical Corporation||Methods for providing steel-on-steel friction and/or steel-on-paper friction with lubricant compositions for power transmitting fluids|
|US20030173251 *||Dec 2, 2002||Sep 18, 2003||Antonio Gutierrez||Hydroxy aromatic mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions|
|US20040147410 *||Jan 13, 2004||Jul 29, 2004||Milner Jeffrey L||Extended drain, thermally stable, gear oil formulations|
|US20050065043 *||Sep 23, 2003||Mar 24, 2005||Henly Timothy J.||Power transmission fluids having extended durability|
|US20050070446 *||Sep 25, 2003||Mar 31, 2005||Ethyl Petroleum Additives, Inc.||Boron free automotive gear oil|
|US20050101494 *||Nov 10, 2003||May 12, 2005||Iyer Ramnath N.||Lubricant compositions for power transmitting fluids|
|US20050101496 *||Nov 6, 2003||May 12, 2005||Loper John T.||Hydrocarbyl dispersants and compositions containing the dispersants|
|US20050143265 *||Dec 31, 2003||Jun 30, 2005||Loper John T.||Hydrocarbyl dispersants including pendant polar functional groups|
|US20050181959 *||Feb 17, 2004||Aug 18, 2005||Esche Carl K.Jr.||Lubricant and fuel additives derived from treated amines|
|US20050192185 *||Feb 27, 2004||Sep 1, 2005||Saathoff Lee D.||Power transmission fluids|
|US20050202979 *||Mar 9, 2005||Sep 15, 2005||Ethyl Petroleum Additives, Inc.||Power transmission fluids with enhanced extreme pressure characteristics|
|US20060003905 *||Jul 2, 2004||Jan 5, 2006||Devlin Cathy C||Additives and lubricant formulations for improved corrosion protection|
|US20060025314 *||Oct 11, 2004||Feb 2, 2006||Afton Chemical Corporation||Power transmission fluids with enhanced extreme pressure and antiwear characteristics|
|US20060217273 *||Mar 22, 2006||Sep 28, 2006||Nubar Ozbalik||Lubricating compositions|
|US20060223716 *||Apr 4, 2005||Oct 5, 2006||Milner Jeffrey L||Tractor fluids|
|US20060264339 *||May 19, 2005||Nov 23, 2006||Devlin Mark T||Power transmission fluids with enhanced lifetime characteristics|
|US20070054813 *||Oct 25, 2006||Mar 8, 2007||Chip Hewette||Boron free automotive gear oil|
|US20070111906 *||Nov 12, 2005||May 17, 2007||Milner Jeffrey L||Relatively low viscosity transmission fluids|
|US20080009426 *||Aug 15, 2007||Jan 10, 2008||Iyer Ramnath N||Lubricant Compositions and Methods Comprising Dispersant and Detergent|
|US20080015124 *||Jul 14, 2006||Jan 17, 2008||Devlin Mark T||Lubricant composition|
|US20080015125 *||Jul 14, 2006||Jan 17, 2008||Devlin Mark T||Lubricant compositions|
|US20080015127 *||Jul 14, 2006||Jan 17, 2008||Loper John T||Boundary friction reducing lubricating composition|
|US20080051305 *||Aug 28, 2006||Feb 28, 2008||Devlin Mark T||Lubricant composition|
|US20080119377 *||Nov 22, 2006||May 22, 2008||Devlin Mark T||Lubricant compositions|
|US20080274921 *||Jun 14, 2007||Nov 6, 2008||Ian Macpherson||Environmentally-Friendly Lubricant Compositions|
|US20090011963 *||Jul 6, 2007||Jan 8, 2009||Afton Chemical Corporation||Truck fleet fuel economy by the use of optimized engine oil, transmission fluid, and gear oil|
|US20090065744 *||Feb 21, 2007||Mar 12, 2009||Basf Se||Use of polynuclear phenolic compounds as stabilisers|
|US20090071067 *||Sep 17, 2007||Mar 19, 2009||Ian Macpherson||Environmentally-Friendly Additives And Additive Compositions For Solid Fuels|
|US20090156445 *||Dec 13, 2007||Jun 18, 2009||Lam William Y||Lubricant composition suitable for engines fueled by alternate fuels|
|US20090233822 *||Feb 17, 2009||Sep 17, 2009||Afton Chemical Corporation||Ultra-low sulfur clutch-only transmission fluids|
|US20090233823 *||Mar 10, 2009||Sep 17, 2009||Volkswagen Aktiengesellschaft||Method for lubricating a clutch-only automatic transmission component requiring lubrication|
|US20100152078 *||Feb 12, 2010||Jun 17, 2010||Ian Macpherson||Environmentally-friendly lubricant compositions|
|US20100279901 *||Nov 4, 2010||Iyer Ramnath N||Methods for providing steel-on-steel friction and/or steel-on-paper friction with lubricant compositions for power transmitting fluids|
|US20110113678 *||May 19, 2011||Basf Se||Use of polynuclear phenolic compounds as stabilisers|
|CN101389738B||Feb 21, 2007||May 15, 2013||巴斯夫欧洲公司||Use of polynuclear phenolic compounds as stabilisers|
|DE102009001301A1||Mar 3, 2009||Sep 24, 2009||Audi Ag||Verfahren zum Schmieren einer Komponente nur für die Kupplung eines automatischen Getriebes, welche Schmierung erfordert|
|DE102009012567A1||Mar 11, 2009||Oct 1, 2009||Afton Chemical Corp.||Clutch-only transmission fluid useful for lubrication comprises oil formulated with additive components having metal detergent, phosphorus-based wear preventative, phosphorylated and boronated dispersant, sulfurized extreme pressure agent|
|EP0267668A2 *||Jun 24, 1987||May 18, 1988||Imperial Chemical Industries Plc||Tri- or tetra-2-hydroxybenzyl-1,2-diaminoalkane derivatives, process for their preparation and their use for extraction of gallium|
|EP0558835A1||Jan 30, 1992||Sep 8, 1993||Albemarle Corporation||Biodegradable lubricants and functional fluids|
|EP0713908A1||Nov 21, 1995||May 29, 1996||Ethyl Corporation||Power transmission fluids|
|EP1568759A2||Feb 24, 2005||Aug 31, 2005||Afton Chemical Corporation||Power transmission fluids|
|EP1669435A1||Dec 9, 2005||Jun 14, 2006||Afton Chemical Corporation||Dispersant reaction product with antioxidant capability|
|EP2017329A1||Apr 17, 2008||Jan 21, 2009||Afton Chemical Corporation||Environmentally-Friendly Lubricant Compositions|
|EP2025737A1||Jul 30, 2008||Feb 18, 2009||Afton Chemical Corporation||Environmentally-friendly fuel compositions|
|EP2072611A1||Nov 11, 2008||Jun 24, 2009||Afton Chemical Corporation||Lubricant composition suitable for engines fueled by alternate fuels|
|EP2230292A1||Nov 8, 2004||Sep 22, 2010||Afton Chemical Corporation||Methods of lubricating transmissions|
|EP2239258A2 *||Jul 18, 2006||Oct 13, 2010||Basf Se||Tetrahydrobenzoxazine|
|EP2267104A2 *||Feb 21, 2007||Dec 29, 2010||Basf Se||Use of polynuclear phenolic compounds as dispersants|
|EP2420553A1||Apr 17, 2008||Feb 22, 2012||Afton Chemical Corporation||Environmentally-Friendly Lubricant Compositions|
|WO2002059240A2 *||Dec 5, 2001||Aug 1, 2002||Infineum International Limited||Hydroxy aromatic mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions|
|WO2002059240A3 *||Dec 5, 2001||May 13, 2004||Infineum Int Ltd||Hydroxy aromatic mannich base condensation products and the use thereof as soot dispersants in lubricating oil compositions|
|WO2007099048A2 *||Feb 21, 2007||Sep 7, 2007||Basf Se||Use of polynuclear phenolic compounds as stabilisers|
|WO2007099048A3 *||Feb 21, 2007||Nov 15, 2007||Basf Ag||Use of polynuclear phenolic compounds as stabilisers|
|U.S. Classification||508/558, 564/369, 564/370, 564/368, 564/367, 564/321|
|Cooperative Classification||C10M1/08, C10M2217/042, C10M2215/26, C10M2217/043, C10M2217/046, C10M2215/062, C10N2270/02, C10M2217/06, C10N2240/02, C10M2215/04|