Organic compositions useful as additives for fuels and lubricants

Compositions useful as additives for fuels and lubricants can be made by reacting (A) an aromatic compound having an OH or SH group attached to an aromatic nucleus and an aromatic hydrogen atom (e.g., a substituted phenol wherein the substituent is an alkyl group of at least 50 carbon atoms); (B) an aldehyde or reactive equivalent thereof (e.g., formaldehyde); (C) a non-amino hydrogen, active hydrogen compound (e.g., a phenol, N,N-dimethyl aniline, etc.) and optionally, (D) an aliphatic alkylating agent of at least 12 carbon atoms (e.g., a polyisobutene of about 50 carbon atoms).

BACKGROUND OF THE INVENTION 
(1) Field of the Invention 
This invention relates to compositions especially useful as additives in 
lubricants based on oils of lubricating viscosity and normally liquid 
fuels. More particularly, it relates to additive compositions prepared by 
reacting a hydroxy aromatic compound (or thiol analog thereof) with an 
aldehyde and an active hydrogen compound containing no amino hydrogens. 
Optionally, reaction with an alkylating agent of at least 12 carbon atoms 
can also be included in the sequence of reactions. 
This invention also pertains to lubricant, normally liquid fuel and 
additive concentrate compositions containing these additive compositions. 
Sulfurized compositions made by sulfurizing the additive compositions of 
this invention with elemental sulfur are also useful as additives for 
lubricants and normally liquid fuels and are within the scope of this 
invention, as are fuel, lubricant and concentrate compositions containing 
them. 
(2) Prior Art 
British Pat. No. 1,173,975 discloses pour point depressants made by 
condensing formaldehyde with an alkylated phenol wherein the alkyl group 
contains at least 18 carbon atoms. 
U.S. Pat. No. 2,440,909 discloses phenolic condensation products made by 
reacting various phenols with 2,6-dimethylol-4-octyl phenol. 
U.S. Pat. No. 3,737,465 discloses condensates of formaldehyde with 
alkyl-substituted phenols wherein the alkyl group ranges in molecular 
weight from 400 to about 5000. These condensates are said to be useful as 
intermediates for reaction with polyamines containing at least two 
##STR1## 
groups. 
The Mannich reaction between active hydrogen compounds, aldehyde such as 
formaldehyde and compounds containing 
##STR2## 
groups has been known for some time. It is also known (e.g., from U.S. 
Pat. Nos. 3,368,972 and 3,649,229) that Mannich condensation products 
derived from certain alkyl phenols can be useful as dispersants in 
lubricating oils and fuels. 
(3) General Background 
The improvement of the performance characteristics of lubricants based on 
oils of lubricating viscosity (e.g., oils and greases) and normally liquid 
fuels through the use of additives has been known for several decades. 
Among the properties that can be improved through the use of additives are 
(1) the ability of a lubricant or fuel to disperse sludge which 
accumulates in it during storage or use, (2) the ability of the fuel or 
lubricant to prevent or inhibit the accumulation of resinous oxidation 
products (e.g., varnish) and carbon deposits on interior engine parts such 
as pistons, cylinder walls, cylinder piston rings, etc. and (3) the 
ability of the lubricant or fuel to inhibit corrosion of metals and other 
materials with which it comes in contact. In these days of material 
shortages, spiraling equipment replacement costs, increasing fuel and 
lubricant costs, and environmental consciousness, the desire to develop 
new, effective, alternate lubricating and fuel additives has continued 
unabated. 
(4) Objects 
Therefore, it is an object of this invention to provide novel compositions 
of matter that will impart useful and desirable properties to lubricants 
and normally liquid fuels containing them. 
It is a further object of this invention to provide novel concentrates, and 
lubricants and fuels containing the novel compositions of matter of this 
invention. 
Other objects will be apparent to those skilled in the art upon review of 
the present specification. 
SUMMARY OF THE INVENTION 
The objects of this invention are accomplished by providing a novel 
composition of matter made by reacting: 
(A) at least one aromatic compound having (i) one or more XH groups, 
wherein X is an oxygen or sulfur atom, directly bonded to a carbon atom of 
an aromatic nucleus and (ii) at least one hydrogen atom bonded directly to 
a carbon atom of an aromatic nucleus; 
(B) at least one aldehyde or reactive equivalent thereof; 
(C) at least one non-amino hydrogen, active hydrogen compound; and 
optionally, 
(D) at least one hydrocarbon-based aliphatic alkylating agent of at least 
about twelve carbon atoms; with the provisos that 
(a) when neither of (A) nor (C) has a hydrocarbon-based aliphatic 
substituent of at least about twelve carbon atoms, then (A) and (C) are 
further characterized by having together a total of at least three 
hydrogen atoms directly bonded to carbon atoms of an aromatic nucleus with 
at least one such hydrogen atom being in each of (A) and (C), and (D) is a 
necessary reactant; and 
(b) when (A) or (C) does contain a hydrocarbon-based aliphatic substituent 
of at least about twelve carbon atoms, then (A) is not (C). 
Novel sulfurized compositions of matter made by sulfurizing the 
afore-described inventive compositions with elemental sulfur are also 
within the scope of this invention, as are lubricants based on oils of 
lubricating viscosity, fuels based on normally liquid fuels and additive 
concentrates containing either or both of these novel compositions of 
matter. 
DETAILED DESCRIPTION OF THE INVENTION 
The Aromatic Compound (A) 
The aromatic compound (A) used in making the compositions of this invention 
has (i) one or more XH groups, wherein X is an oxygen or divalent sulfur 
atom, directly bonded to a carbon atom of an aromatic nucleus and (ii) at 
least one aromatic hydrogen atom. Metal salts of (A) can also be used, 
particularly of the Group IA and IIA metals. Usually these aromatic 
compounds have one to three XH groups; more typically they have one XH 
group. Generally X is oxygen and thus the XH group is a hydroxyl group. 
The aromatic nucleus can be a single-ring nucleus such as a benzene ring, a 
pyridine ring, a thiophene ring, etc., or a multi-ring aromatic nucleus. 
Such multi-ring nuclei can be of the fused type (e.g., naphthalene, 
anthracene, indolyl, etc.) or they can be of the bridged type, wherein 
individual aromatic rings are linked through bridging linkages to each 
other. Such bridging linkages can be chosen from the group consisting of 
carbon-to-carbon single bonds, ether linkages, sulfide linkages, 
polysulfide linkages of 2-6 sulfur atoms, sulfinyl linkages, sulfonyl 
linkages, methylene linkages, lower alkylene linkages, di(lower 
alkyl)-methylene linkages, lower alkylene ether linkages, lower alkylene 
sulfide linkages, lower alkylene polysulfide linkages of 2 to 6 sulfur 
atoms, and mixtures of such bridging linkages. 
When linkages are present in the aromatic nuclei, there are usually no more 
than five such linkages per nucleus; generally, however, the aromatic 
nuclei of (A) are single ring nuclei or fused ring nuclei of up to four 
rings. 
The aromatic compounds (A) used in making the compositions of this 
invention have at least one aromatic hydrogen atom (that is, a hydrogen 
atom bonded directly to a carbon atom of an aromatic nucleus). Usually, 
there are two or more aromatic hydrogen atoms present. For reasons of 
cost, availability, and performance, the most typical aromatic nucleus of 
(A) is a benzene nucleus, although substituted benzenes and substituted 
naphthalenes are also useful. When substituents are present in the 
aromatic nucleus of (A) they are selected from the group consisting of 
lower alkyl, lower alkoxyl, halo, lower alkyl mercapto, cyano and 
combinations thereof. 
Specific examples of single ring aromatic nuclei include the following: 
##STR3## 
etc. wherein Me is methyl, Et is ethyl, Pr is n-propyl and Cl is chlorine. 
Examples of poly-fused ring aromatic nuclei include the following: 
##STR4## 
etc. 
Specific examples of linked poly-ring aromatic nuclei include the 
following: 
##STR5## 
In certain embodiments of this invention, the aromatic compound (A) does 
not have at least one hydrocarbon-based substituent of at least twelve 
carbon atoms. When this is so, (D) (which is discussed in greater detail 
hereinbelow) is a necessary reactant to make the compositions of this 
invention, and the total number of aromatic hydrogen atoms in reactants 
(A) and (C) is at least three, more preferably, at least five. Specific 
examples of aromatic compounds (A) not having a hydrocarbon-based 
substituent of at least 12 carbon atoms include phenol, substituted 
phenols wherein the substituents are chosen from the group consisting of 
lower alkyl, lower alkoxyl, halo, lower alkyl mercapto, cyano and 
combinations thereof, resorcinol, o- and/or p-hydroquinones, the various 
naphthanols, anthracenols and substituted analogs thereof wherein the 
substituents are chosen from the group consisting of lower alkyl, lower 
alkoxyl, halo, lower alkyl mercapto, cyano and combinations thereof. In 
this specification and the appended claims, "lower" refers to groups 
having less than eight carbon atoms. 
In other embodiments of this invention, the aromatic compound (A) has a 
hydrocarbon-based aliphatic substituent of at least 12 carbon atoms. Often 
this substituent has at least about 30 carbon atoms. In such embodiments, 
(D) is an optional reactant. The nature of this substituent is generally 
the same as that of the reagent (D) which is discussed hereinbelow, and 
usually the substituent is derived from such a reagent as described 
hereinbelow. 
Usually, this substituent is purely aliphatic and contains no more than one 
carbon-to-carbon double bond (that is, an ethylenic linkage 
##STR6## 
per every ten carbon-to-carbon single bonds. The substituent is preferably 
free from acetylenic unsaturation (that is, --C.tbd.C--). Often it has at 
least about thirty carbon atoms. Typically, the substituent has an average 
of no less than about 50 carbon atoms and an average of no more than about 
10,000 carbon atoms. Usually, it has an average of no more than 300 carbon 
atoms. 
A preferred type of aromatic compound (A) having a substituent of at least 
12 carbon atoms is a mono-substituted phenol of the general formula: 
##STR7## 
wherein R is a hydrocarbon-based aliphatic substituent of about 30 to 
about 5,000 carbon atoms. Usually R in Formula 1 is derived from a homo- 
or interpolymer of mono-olefins having from 2 to about 20 carbon atoms and 
is in a position para to the --OH group. Specific examples of the 
substituent R are a polypropylene group of about 60 to 340 carbons, a 
poly(ethylene/propylene) group of about 110 to about 260 carbons 
(equimolar monomer ratio), a poly(isobutene) group of about 70 to about 
320 carbon atoms, and a poly(1-hexene/1-octene/1-decene) group of about 
400 to about 750 carbons (equimolar monomer ratios). 
A preferred source of the group R are polybutenes, especially 
poly(isobutene)s, obtained by polymerization of a C.sub.4 refinery stream 
having a total butene content of 20 to 75 weight percent and, more 
specifically, isobutene content of 15 to 60 weight percent in the presence 
of a Lewis acid catalyst such as aluminum trichloride or boron 
trifluoride. The balance of the stream can contain materials such as 
ethylene, propylene, butadiene and the saturated analogs as well as other 
materials typically found in C.sub.4 refinery streams. These polybutenes 
contain predominantly (greater than 80% of total repeat units) isobutene 
repeating units of the configuration 
##STR8## 
The attachment of the hydrocarbyl group R to the aromatic ring of compound 
(A) can be accomplished by a number of techniques well known to those 
skilled in the art. A number of these are discussed herein below. Suffice 
it to say at this point that one particularly suitable technique is the 
Friedel-Crafts reaction, wherein an olefin (e.g., a polymer containing an 
olefinic bond), or halogenated or hydrohalogenated analog thereof, is 
reacted with a phenol. The reaction occurs in the presence of a Lewis acid 
catalyst (e.g., boron trifluoride and its complexes with ethers, phenols, 
hydrogen fluoride, etc., aluminum chloride, aluminum bromide, and zinc 
dichloride). Methods and conditions for carrying out such reactions are 
well known to those skilled in the art. See, for example, the discussion 
in the article entitled, "Alkylation of Phenols" in "Kirk-Othmer 
Encyclopedia of Chemical Technology," Second Edition, Vol. 1, pages 
894-895, Interscience Publishers, a division of John Wiley and Company, 
N.Y., 1963. 
When the aromatic compound (A) has at least one hydrocarbon-based 
substituent of at least 12 carbon atoms, the reagent (D) may or may not be 
used to produce the compositions of this invention. Often, the reagent (D) 
is not used in these embodiments. Since the typical hydrocarbon-based 
substituents incorporated in the aromatic compound (A) having at least 12 
aliphatic carbon atoms are derived from the hereinafter described reagent 
(D), all the preferences expressed during the discussion of (D) apply 
equally to the hydrocarbon-based substituents of (A) having at least 12 
aliphatic carbon atoms. 
Mixtures of two or more of the above-described aromatic compounds can be 
used as the aromatic compound (A) reagent. 
The Aldehyde or Reactive Equivalent Thereof (B) 
The aldehyde (B) is generally a mono- or dialdehyde of 1 to 30 carbon 
atoms; usually (B) is a lower hydrocarbon-based aldehyde such as glyoxal, 
acetaldehyde, propanal, butanal, glutaric aldehyde, etc., having up to 7 
carbon atoms. Because of cost, availability and reactivity, the aldehyde 
(B) is preferably a mono-aldehyde and most preferably, it is formaldehyde 
or reactive equivalent thereof. 
Exemplary of such lower aldehydes are formaldehyde, acetaldehyde, the 
butyraldehydes, hydroxybutyraldehydes (e.g., those formed by condensation 
of two moles of acetaldehyde), the pentanals, hexanals and heptanals. 
Other suitable aldehydes are carbocyclic aldehydes such as benzaldehyde, 
furfural, phenyl acetaldehyde, cyclohexane carboxaldehyde, fural, etc. 
Substituted aldehydes such as orthohydroxybenzaldehydes, salicylaldehyde, 
chloral, chloroacetaldehyde and hydroxy acetaldehyde can also be used as 
can be methoxy and nitro analogs thereof. Mixtures of the above-mentioned 
aldehydes can also be used as reagent (B) in the formation of the 
compositions of this invention. 
The aldehyde (B) or a portion thereof can be replaced by a reactive 
equivalent thereof. Reactive equivalents are materials which generate 
aldehydes under the conditions of the reaction to which the equivalent is 
subjected. Typical reactive equivalents of the aldehyde are polymers such 
as cyclic oligomers and linear high polymer of the aldehyde (e.g., 
trioxane and paraformaldehyde are reactive equivalents of formaldehyde) or 
solutions of aldehydes in solvents such as water and lower alkanols. 
Acetals such as methal can also be considered reactive equivalents of 
formaldehyde. 
The Non-amino Hydrogen, Active Hydrogen Compound (C) 
The non-amino hydrogen, active hydrogen compound (C) is an organic compound 
which does not contain any &gt;NH groups. These compounds can, however, 
contain NZ.sub.2 groups, wherein each Z is a hydrocarbon-based radical; in 
other words, tertiary amine-containing compounds are considered non-amino 
hydrogen compounds. 
These active hydrogen compounds are compounds capable of forming Mannich 
bases as defined in "Advanced Organic Chemistry: Reactions, Mechanism and 
Structure" by Jerry March, published by McGraw-Hill Book Company, 1968, 
N.Y. on pages 670-672, or they are aromatic compounds bearing at least one 
electron-donating substituent having a negative sigma (para) value as 
defined by the Hammett function set forth in "Physical Organic Chemistry," 
Second Edition, L. P. Hammett, McGraw-Hill Book Company, N.Y., 1970. These 
references are hereby incorporated by reference for their disclosures of 
parameters which define the active hydrogen compounds (C). Regardless of 
type, the active hydrogen compounds (C) all contain at least one hydrogen 
atom which is capable of reacting with the hydrocarbon-based aldehyde (B). 
When the aromatic compound (A) or the active hydrogen compound (C) contains 
a hydrocarbon-based aliphatic substituent of about 12 carbon atoms, the 
active hydrogen compound (C) is not the same as the aromatic compound (A), 
although there may be a generic relationship between the two. Thus, for 
example, when the aromatic compound (A) is of the formula 
##STR9## 
wherein R.degree. is a hydrocarbon-based aliphatic group of 30 to 200 
carbon atoms, the active hydrogen compound (C) can be of the formula 
##STR10## 
wherein R* is of 50 to 100 carbon atoms and R.degree. is not the same as 
R*. For example, R.degree. could contain an average of 35 carbon atoms 
while R* contains an average of 70 carbon atoms. Alternatively, both 
R.degree. and R* could both contain an average of 70 carbon atoms, but 
R.degree. could be derived from poly(hexene-1) while R* is derived from 
poly(isobutene). 
Examples of the types of compounds which can serve as the active compound 
(C) in reactions forming the compositions of this invention are the 
following: 
(a) phenols including those with at least one R' substituent such as 
phenol; resorcinol; o- and p-hydroquinone (and the C.sub.1-30 
hydrocarbon-substituted analogs thereof); anisole; pyrogallol; catechol; 
the various xylenols; o-, m- and p-cyanophenols; o-, m- and p-chloro and 
bromo phenols; the biphenyldiols and -triols, the pyridinols, 
4,4'-isopropylidenebisphenols, etc.; 
(b) naphthols including those with at least one R' substituent such as 2-, 
3- and 4-naphthol; the azanaphthalenols, -diols and -triols and chloro-, 
bromo-, and cyano-substituted analogs thereof; 
(c) ethers of the formula 
EQU (R').sub.2 CHOR" 
such as dimethyl, diethyl-, dipropyl-, di(isobutyl)-, etc., ethers; benzyl 
alkyl ethers; dibenzyl ethers; alkyl phenyl and alkyl naphthyl ethers, 
etc.; 
(d) ketones of the formula 
EQU (R').sub.2 CHC(O)R" 
such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 
cyclohexanone, acetophenone and analogous C.sub.3-30 alkyloyl benzenes and 
naphthalenes, etc.; 
(e) diones of the formula 
EQU (R').sub.2 CHC(O)CR'.sub.2 C(O)R" 
such as 2,4-pentanedione, 3,5-hexanedione; 2,4-, 3,5-, 4,6-decanediones, 
etc.; 
(f) alcohols of the formula 
EQU YOH 
such as the C.sub.6-30 alkanols and alkenols as well as the phenyl- and 
naphthyl-substituted analogs thereof (e.g., 1-hexanol, benzyl alcohol, 
n-dec-2-en-6-ol, etc.); 
(g) carboxylic acids of the formula 
EQU (R').sub.2 CHC(O)OH 
and thiol analogs thereof, such as the saturated and unsaturated C.sub.1-30 
fatty acids and their phenyl-, naphthyl-, xylyl-, and tolyl-substituted 
analogs thereof (e.g., acetic, butyric, myristic, oleic, stearic, 
linoleic, phenyl acetic acids, etc.); 
(h) carboxylate esters of the formula 
EQU (R').sub.2 CHC(O)OR" 
and thiones and thiol analogs thereof, such as alkyl, alkenyl, phenyl, 
naphthyl, alkyl-substituted phenyl and -naphthyl esters of the acids 
mentioned under (g) above (e.g., n-octyl acetate, hexadecenyl butyrate, 
methyl phenyl acetate, etc.); 
(i) nitriles of the formula 
EQU (R').sub.2 CHCN 
such as the C.sub.1-30 alkyl, alkenyl, phenyl- and naphthyl-substituted 
alkyl and alkenyl nitriles (e.g., acetonitrile, ethyl nitrile, cinnamic 
nitrile, phenyl acetonitrile, etc.); 
(j) substituted heterocyclic compounds of the formula 
EQU heterocycle--CH(R').sub.2 
such as the C.sub.1-30 alkyl and alkenyl-substituted thiophenes, pyrroles, 
furans, pyridines, pyrans, dioxanes, N-C.sub.1-30 alkyl and alkenyl 
pyrroles and imidazoles; quinolines, etc.); 
(k) tertiary aromatic amines of the formula 
EQU (R.sup.#).sub.3 N 
such as di-(C.sub.1-30 alkyl and alkenyl)phenyl and naphthyl amines, etc. 
(e.g., N,N-dimethylnaphthylamine, triphenylamine, N,N-dimethyl aniline, 
etc.); 
(l) tertiary aromatic polyamines of the formula 
##STR11## 
such as the N-peralkylated polyalkylene polyamines and phenylene diamines 
(e.g., N,N',N'-trimethyl-N-phenyl ethylene diamine, 
N,N'-tetra-ethyl-p-phenylene diamines, etc.); 
(m) glycols and polyglycol ethers of the formula 
EQU R'O (AO).sub.n' R' 
such as the C.sub.2-30 alkylene and polyalkylene glycols and polyglycols 
(e.g., ethylene glycol, di(propylene)glycol, trimethylene glycol; 
2,7-decane diol, penta(oxyethylene)glycol, deca(oxypropylene)glycol, 
etc.); 
(n) hydroxy hydrocarbyl tertiary amines of the formula 
EQU R'"(OH).sub.p' (NR").sub.q' 
such as the tertiary alkanol and alkenol amines and their aromatic analogs 
(e.g., N,N-di(C.sub.1-30 alkyl)ethanol amines; N,N-di-(C.sub.1-30 hydroxy 
alkyl)phenyl amines, etc.); and 
(o) polyols of the formula 
EQU R'"(OH).sub.m' 
such as the C.sub.5-30 poly(methylol)alkanes (e.g., pentaerythritol, 
trimethylolethane and trimethylolpropane, etc.), glycerol, erythritol, 
sorbitol, mannitol, etc.; wherein each R' is independently hydrogen or R"; 
each R" is independently a C.sub.1 to C.sub.30 hydrocarbon-based 
substituent, R.sup.# is R" with the proviso that at least one R" per 
molecule is a C.sub.6 to C.sub.18 aromatic substituent (preferably purely 
hydrocarbyl in nature); A is a divalent hydrocarbon-based group of 2 to 30 
carbon atoms and especially alkylene of two to six carbon atoms, n' is an 
integer of 1 to 10; m' is an integer of 3 to 6; R'" is a polyvalent 
C.sub.3-30 hydrocarbon-based non-aromatic group (e.g., aliphatic or 
alicyclic) having m' valences; p' and q are each 1, 2 or 3, their sum 
being m'; and Y is an alkyl or alkenyl group of about 6-30 carbon atoms. 
Where structurally possible, 2R', 2R", or an R' and an R" group(s) can 
together form a carbocyclic ring on 4 to 7 ring carbon atoms. Thio and 
thiol analogs (wherein one or more oxygen atoms in the above formulae are 
replaced by sulfur atoms) of the above-described active hydrogen compounds 
can also be used as reactant (C) as can mixtures of such active hydrogen 
compounds including mixtures of oxygen and sulfur analogs. 
When (A) has a hydrocarbon-based substituent of at least 12 carbon atoms 
and (D) is not a reactant, the preferred active hydrogen compound (C) are 
phenols (including benzene diols such as resorcinol and the 
hydroquinones), naphthols, tertiary aromatic amines, carboxylic acids or 
thiol analogs of said phenols, naphthols or acids. 
When the alkylating reagent (D) is a necessary reactant, the preferred 
active hydrogen compounds (C) are phenols, naphthols, and tertiary 
aromatic amines. 
The Hydrocarbon-based Alkylating Agent (D) 
The hydrocarbon-based aliphatic alkylating agent (D) has at least 12 carbon 
atoms. Generally, (D) has an average of about 30 to about 10,000 carbon 
atoms. Often (D) has no less than an average of about 50 carbon atoms and 
no more than an average of about 300 carbon atoms. 
As used herein, the term "hydrocarbon-based" denotes a substituent or agent 
which, respectively, has a carbon atom directly attached to the remainder 
of the molecule and has predominantly hydrocarbyl character within the 
context of this invention or which is an agent capable of introducing such 
a hydrocarbon-based substituent into a molecule. Examples of such 
substituents include the following: 
(1) Aliphatic (e.g., alkyl or alkenyl) substituents. 
(2) Substituted hydrocarbon substituents, that is, those containing 
non-hydrocarbon radicals which, in the context of this invention, do not 
alter the predominantly hydrocarbyl character of the substituent. Those 
skilled in the art will be aware of suitable radicals (e.g., hydroxy, halo 
(especially chloro and fluoro), alkoxyl, mercapto, alkyl mercapto, 
sulfoxy, etc., radicals). 
(3) Hetero substituents, that is, substituents which, while predominantly 
hydrocarbon in character within the context of this invention, contain 
atoms other than carbon present in a chain otherwise composed of carbon 
atoms. Suitable hetero atoms will be apparent to those skilled in the art 
and include, for example, sulfur, oxygen and nitrogen and form 
substituents such as, e.g., aza, oxa and thia substituents. 
In general, no more than about three non-hydrocarbon radicals or hetero 
atoms, and usually no more than one, will be present for each 10 carbon 
atoms in the hydrocarbon-based substituent. Usually no non-hydrocarbon or 
hetero atoms are present and the hydrocarbon substituent is purely 
hydrocarbyl. 
Generally, the hydrocarbon-based substituents in the compositions of this 
invention are free from acetylenic unsaturation. Ethylenic unsaturation, 
when present, preferably will be such that no more than one ethylenic 
linkage will be present for every 10 carbon-to-carbon bonds in the 
substituents. 
The alkylating agent (D) is aliphatic in character. This means it contains 
no more than one non-aliphatic (e.g., carbocyclic group) for every 15 
aliphatic carbon atoms. Generally (D) is purely aliphatic in nature and 
contains no carbocyclic groups or heterocyclic groups. 
The alkylating agents (D) used to make the compositions of this invention, 
can be either olefins or halides derived from said olefins by the addition 
of a hydrohalide or halogen such as bromine or chlorine. Such halides can 
also be obtained by halogenation of appropriate saturated or unsaturated 
hydrocarbons (e.g., by free radical halogenation). Useful olefins are, for 
the most part, high molecular weight substantially saturated petroleum 
fractions (e.g., cracked waxes) or substantially saturated olefin 
oligomers and polymers, particularly oligomers and polymers of 
mono-olefins having from 2 to about 30 carbon atoms. Exemplary of polymers 
useful as the alkylating agent (D) are the homopolymers of 1-mono-olefins 
having 2 to about 20 carbon atoms such as ethylene, propene, 1-butene, 
isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene, 
2-methyl-5-propyl-1-hexene, 1-dodecene, 1-tetradecene, 1-octadecene, 
1-cosene, 1-tetracosene, etc. 
Homopolymers of medial olefins, i.e., olefins in which the olefinic linkage 
is not at the terminal position, likewise are useful. They are illustrated 
by 2-butene, 3-pentene, and 4-octene. Mixtures of these homopolymers such 
as a mixture of poly(propene) and poly(1-decene) can also serve as the 
alkylating agent (D). 
Also useful are the interpolymers of olefins, such as those mentioned 
above, with other interpolymerizable olefinic substances such as aromatic 
olefins, cyclic olefins, and polyolefins. Such interpolymers include, for 
example, those prepared by polymerizing isobutene with styrene; isobutene 
with butadiene; propene with isoprene; ethylene with piperylene; isobutene 
with 1-tetradecene; isobutene with p-methyl styrene; 1-hexene with 
1,3-hexadiene; 1-octene with 1-hexene; 1-heptene with 1-pentene; 
3-methyl-1-butene with 1-octene; 3-3-dimethyl-1-pentene with 1-hexene; 
isobutene with styrene and piperylene; etc. 
Mixtures of such interpolymers as well as mixtures of one or more 
interpolymer with one or more homopolymer can also serve as the alkylating 
agent (D). 
Specific examples of such interpolymers include copolymer of 95% (by 
weight) of isobutene with 5% of styrene; terpolymer of 98% of isobutene 
with 1% of piperylene and 1% of chloroprene; terpolymer of 95% of 
isobutene with 2% of 1-butene and 3% of 1-hexene; terpolymer of 60% of 
isobutene with 20% of 1-pentene and 20% of 1-octene; copolymer of 80% of 
1-hexene and 20% of 1-heptene; terpolymer of 90% of isobutene with 2% of 
cyclohexene and 8% of propene; and copolymer of 80% of ethylene and 20% of 
propene. 
Typical of the alkylating agents (D) are the homo- and interpolymers of the 
various butenes (i.e., isobutene, 1- and 2-butene) and mixtures thereof. 
Particularly preferred sources are the butene polymers described 
hereinabove wherein isobutene units 
##STR12## 
predominate, preferably to the extent of about 80% of the molecule's 
units. These butene polymers usually yield polybutenyl substituents. 
For the lower molecular weight alkylating agent (D) (e.g., those of less 
than about 50 carbon atoms), pure olefins and mixtures of such pure 
olefins (or their halogenated or hydrohalogenated analogs) can be used. 
Exemplary of such alkylating agents are 1-octadecene, 1-tetracontene, 
1-contene, 2-dodecene, etc. 
Further specific examples of (D) are the following: tetra(propylene), 
tri(isobutene), 3-hexacontene, 1-henpentacontene, a mixture of 
poly(ethylene/propylene) polymers having about 35 to about 70 carbon 
atoms, a mixture of the oxidatively or mechanically degraded 
poly(ethylene/propylene) polymers having about 35 to about 70 carbon 
atoms, a mixture of poly(propylene/1-hexene) polymers of about 80 to about 
150 carbon atoms, a mixture of poly(isobutene) polymers having between 20 
and 32 carbon atoms and a mixture of polyisobutene polymers having an 
average of 50 to 75 carbon atoms. 
As noted above, when (A) or (C) has a hydrocarbon-based substituent of at 
least twelve carbon atoms, that substituent is essentially aliphatic and, 
in general, is the same as the substituent that is introduced by the 
alkylating agent (D). Therefore, it will be obvious to those skilled in 
the art that the above description of (D), with all the included 
limitations, exemplifications and preferences applies equally to the 
hydrocarbon-based substituent present in (A) and/or (C) in many 
embodiments of this invention. 
The alkylating agent (D) can be reacted with (A) or (C) or the product of 
(A), (B) and (C) where (A) and/or (C) has a hydrocarbon-based substituent 
of at least about 12 carbon atoms and where neither of them do. In the 
latter case, (D) is a necessary reactant, while in the former case, it is 
an optional reactant. When reagent (A) or (C) has a hydrocarbon-based 
substituent of at least 12 carbon atoms, it is preferred that (D) not be a 
reactant. 
Preferably, the alkylating agent (D) is reacted with the aromatic compound 
(A) or the active hydrogen compound (C) before these reagents are reacted 
with the other reagents used to make the compositions of this invention. 
However, as noted above, it is possible that the alkylating agent (D) can 
be reacted with the product obtained from reaction of (A) with (B) and 
(C). 
The reaction of the alkylating agent (D) with the other reagents used to 
make the compositions of this invention, typically take place under 
Freidel-Crafts conditions, in the presence of a Freidel-Crafts catalyst, 
such as boron trifluoride and its complexes with ether, phenol, hydrogen 
fluoride, etc. Other Freidel-Crafts catalysts such as aluminum chloride, 
aluminum bromide, etc. can also be used. The method and conditions for 
carrying out such reactions are well known in the art. See for example, 
description of such reactions with aromatic compounds in the article 
entitled "Alkylation of Phenols" in Kirk-Othmer "Encyclopedia of Chemical 
Technology," Second Edition, Vol. 1, pages 894-895, Interscience 
Publishers, a division of John Wiley and Company, 1963. Other equally 
appropriate and convenient techniques for the reaction of the alkylating 
agent (D), with the other components used to make the compositions of this 
invention will occur readily to those skilled in the art. 
The sequence in which the various reactants (A), (B), (C) and (D) can be 
reacted to form the compositions of this invention is not critical. 
Therefore, various sequences can be used. For example, (A) can be reacted 
with (D) then with (B) and finally with (C). Alternatively, (A) can be 
reacted with (D) and then the intermediate (A)/(D) product thereby 
obtained reacted with both (B) and (C) simultaneously. In another 
variation, (A) can be reacted with (B) and the intermediate (A)/(B) 
product thereby obtained then reacted with (C), and finally the 
(A)/(B)/(C) product reacted with (D). When (D) is not a reactant (A) can 
first be reacted with (B) and then the (A)/(B) intermediate reacted with 
(C). Alternatively (A), (B) and (C) can be reacted simultaneously. 
In another embodiment of this invention, (A), (B) and (C) can be 
simultaneously reacted and optionally the product thereby obtained then 
reacted with (D). The sequence of reactions is only limited by the fact 
that (A) cannot be reacted with (C) without being first reacted with (B) 
or the reaction being carried out simultaneously with (B), and further, 
that (D) is never directly reacted with (B). Thus, (A) can be reacted with 
(B), then (C) can be reacted with (D) and finally the products (A)/(B) and 
(C)/(D) of each reaction reacted with each other to provide the 
compositions of this invention. 
The ratio of reactants (A), (B), (C) and (D) generally falls in the molar 
ratio of (A):(B):(C):(D) of 1:1-5:1-5:0.0-5. Usually the ratio of 
(A):(B):(C):(D) is 1:1-5:1-5:0.5-5. When (B) is a reactive equivalent of 
an aldehyde, its molecular weight is considered to be the amount of 
aldehyde that it will produce under the conditions of the reaction. Thus, 
trioxane's molecular weight is considered to be one-third of its actual 
molecular weight. The molecular weights of (A), (B) and (C) are their 
conventional molecular weights. Where they contain a mixture of polymeric 
substituents, their number average molecular weight is used. Generally, 
the reactants are reacted in the molar ratio of (A):(B):(C):(D) of 
1:1-3:1-3:0-3; usually 1:1-3:1-3:1-3. 
Generally, the reaction of (A) or (A) derived intermediate (e.g., an 
(A)/(D) intermediate) with (B) takes place in the temperature range of 
about 30.degree. to about 150.degree. C., preferably, about 80.degree. to 
about 100.degree. C. Similarly, the reaction of (C) with the other 
reagents made to make the compositions of this invention or intermediates 
derived from them takes place in the range of about 80.degree. to about 
220.degree. C., preferably about 100.degree. to about 190.degree. C. The 
reaction of (C) is generally accompanied by the production of water which 
is drawn from the reaction mixture, thus driving the reaction to 
completion. This can be accomplished by conventional techniques such as 
azeotropic distillation, vacuum distillation and so forth. 
The times for the reaction of each reagent with each other and the 
intermediates formed thereby generally takes place in a period of time 
which is not critical and ranges from about 0.25 to about 48 hours, 
usually from about 1-8 hours for each step. As is apparent, all that is 
necessary is that each step of the reaction in the sequence of reaction 
steps is carried out for a period of time sufficient to obtain reaction 
between the reactants present in order to form the desired reaction 
product or intermediate. It will be obvious to those skilled in the art 
that intermediate products (e.g., (A)/(B), (C)/(D), (A)/(C), (A)/(D), 
etc.) can be stored for prolonged periods (for example, days, weeks and 
months) before being further reacted. 
A substantially inert, normally liquid organic solvent/diluent is often 
used in these reactions to increase their rate but its use is not 
absolutely necessary. Often excesses of one or more reactants can be used 
for this purpose. Useful organic solvent/diluents include lower alkanols, 
such as butyl and amyl alcohols; aromatic hydrocarbons such as benzene, 
toluene, xylene; aliphatic hydrocarbons such as decane, dodecane; 
kerosene; mineral oil; etc. and mixtures of two or more of any such 
conventional solvent/diluents. As will be apparent, a "substantially 
inert" solvent/diluent is one which does not react with the reactants or 
products in any significant amount and, preferably, not at all. 
The reaction of aldehyde (B) with (A) and/or (C) is usually catalyzed by a 
base or an acid; preferably, the (A)/(B) is catalyzed with a base such as 
an alkali metal or alkaline earth metal oxide, hydroxide or alkoxide such 
as sodium hydroxide, and calcium oxide, potassium hydroxide, calcium 
hydroxide, barium methylate, barium ethoxide, etc. Other suitable basic 
catalyst include tetramethyl ammonium hydroxide, ammonium hydroxide, etc. 
Up to one mole of catalyst for each mole of aldehyde (B) present can be 
used, normally about 0.05-0.5 mole of catalyst per mole of (B) is used. It 
is usually preferable to neutralize the basic catalyst with a low 
molecular weight organic or inorganic acid before proceeding further. 
However, such neutralization is not necessary. Useful acids for 
accomplishing such neutralizations (or catalyzing an (A)/(B) reaction with 
(C)) include the lower alkanoic acids, such as formic acid and acetic 
acid, and inorganic acids such as sulfuric, hydrochloric, phosphoric, 
nitric acid and the like. 
It is believed that the compositions of this invention contain bridges 
derived from the organic residue of the aldehyde (B) linking the organic 
residues of the aromatic compound (A) and the active hydrogen compound 
(C). This belief is supported by the available data. Thus, when (B) is 
formaldehyde, methylene bridges are formed. The invention, however, is in 
no way intended to be limited by reference to such bridges.

The following are specific illustrative examples of how to make and use the 
aforesaid invention and include the best mode of the invention presently 
known. In these examples, as well as in this specification and the 
appended claims, all percentages and parts are by weight (pbw), unless 
otherwise expressly stated to the contrary, and the molecular weights are 
number average molecular weights as determined by vapor pressure osmometry 
(VPO). 
Examples 1 to 13 are carried out according to the following general 
procedure: A mixture of the polybutenyl-substituted phenol, mineral oil, 
n-butanol, sodium hydroxide and paraformaldehyde is heated at 
82.degree.-87.degree. C. for three hours. Glacial acetic acid is then 
added to neutralize the hydroxide catalyst. Distillate is removed as the 
mixture is heated to 125.degree. C. under nitrogen. The active hydrogen 
compound is added and the mixture heated at 175.degree.-185.degree. C. for 
three hours. The reaction product is then stripped at 
190.degree.-200.degree. C. under vacuum and filtered to yield an oil 
solution of the desired product containing about 40% wt. of mineral oil. 
Examples 14 to 18 are carried out by the same procedure with the exception 
that the active hydrogen compound is added immediately after the glacial 
acetic acid addition. 
TABLE I 
__________________________________________________________________________ 
Polybutenyl Solvent Acetic 
Example 
Phenol (CH.sub.2 O).sub.x 
NaOH 
n-butanol 
oil Acid 
Active 
Number 
--Mn* 
pbw pbw equiv. 
pbw pbw equiv. 
Hydrogen Compd. 
pbw 
__________________________________________________________________________ 
1 a 4000 165 0.25 
165 2863 0.25 
phenol 250 
2 b 960 39.6 0.06 
40 701 0.06 
o-chlorophenol 
77.2 
3 c 1800 99 0.15 
99 1318 0.15 
phenol 150 
4 a 960 39.6 0.06 
40 693 0.06 
anisole 64.8 
5 b 960 36 0.06 
36 709 0.06 
.alpha.-naphthol 
87 
6 a 1120 46 0.07 
46 809 0.07 
p-cresol 73 
7 a 960 33 0.06 
40 698 0.06 
N,N-dimethyl 
aniline 72.6 
8 b 1120 46 0.07 
46 828 0.07 
o-t-butyl 
phenol 105 
9 b 715 33 0.05 
33 519 0.05 
o-cresol 52 
10 a 4160 172 0.26 
172 3005 0.26 
catechol 286 
11 b 1120 46 0.07 
46 845 0.07 
bisphenol A** 
106.5 
12 a 960 39.6 0.06 
40 699 0.06 
Pyrogallol 
75.6 
13 b 800 33 0.05 
33 578 0.05 
Hydroquinone 
55 
14 a 1360 56 0.085 
56 976 0.085 
Mercapto acetic 
acid 78 
15 b 1040 43 0.065 
43 762 0.065 
Thiophenol 
82 
16 d 664 165 0.35 
165 851 0.35 
Thiophenol 
550 
17 a 1760 72.6 0.11 
73 1271 0.11 
Resorcinol 
121 
__________________________________________________________________________ 
*--Mn of phenol by VPO; a = 1300; b = 1340; c = 920; and d = 266; 
**4,4'-isopropylidenebisbenzenol 
EXAMPLE 18 
A mixture of 960 parts of a polybutenyl-substitued phenol (Mn(VPO)=1340), 
687 parts of mineral oil, 40 parts n-butanol, 60 parts of phenol, 5.3 
parts of a 50% aqueous solution of sodium hydroxide and 50 parts of 
paraformaldehyde is heated at 175.degree. C. under nitrogen for 6 hours as 
water is removed by azeotropic distillation. Glacial acetic acid (41 
parts) is added to the reaction mixture and the mixture is then stripped 
to 200.degree. C. under vacuum and filtered to yield a 60% solution of the 
desired product in mineral oil. 
EXAMPLE 19 
A mixture of 1600 parts of a polybutenyl-substituted phenol (Mn(VPO)=1300), 
300 parts of xylene, 25 parts of concentrated hydrochloric acid solution 
and 33 parts of paraformaldehyde is heated at 85.degree.-90.degree. C. for 
4 hours. The mixture is stripped to 180.degree. C. under vacuum. Phenol 
(150 parts) is then added and the mixture is heated to 220.degree. C. in 
16 hours. The mixture is stripped at 220.degree. C. under vacuum and 710 
parts of mineral oil is added to the residue. Filtration yields the 
desired product (69.5% solution in mineral oil). 
EXAMPLE 20 
A mixture of 1120 parts of a polybutenyl-substituted phenol (Mn=1340), 498 
parts of mineral oil, 46 parts of n-butanol, 5.6 parts of a 50% aqueous 
solution of sodium hydroxide and 46.2 parts of paraformaldehyde is heated 
at 80.degree.-90.degree. C. for 3 hours. Glacial acetic acid (4.2 parts) 
is then added and the mixture is heated at 110.degree.-115.degree. C. for 
0.5 hour. The reaction mixture is stripped to 126.degree. C. under vacuum 
to yield the desired intermediate. 
A mixture of 240 parts of mineral oil and 221 parts of phenol is heated to 
166.degree. C. At 166.degree.-185.degree. C. 1310 parts of the 
polybutenylphenol-formaldehyde intermediate prepared above is added to the 
mixture over a period of 5 hours and this mixture held at 180.degree. C. 
for 1 hour. The reaction mixture is stripped at 190.degree. C. under 
vacuum to yield 1421 parts of the desired polybutenyl-substituted 
phenol/formaldehyde/phenol product (60% solution in mineral oil). 
EXAMPLE 21 
A mixture of 1064 parts of a tetrapropenyl phenol, 844 parts of mineral 
oil, 264 parts of n-butanol, 32 parts of a 50% aqueous solution sodium 
hydroxide and 264 parts of paraformaldehyde is heated at 85.degree. C. for 
3 hours. Glacial acetic acid (24 parts) followed by 665 parts of a 
tetrapropenyl phenol is added and the mixture is stripped to 122.degree. 
C. At 85.degree. C., 150 parts of phenol is added and then heated to 
169.degree. C. in 6 hours, as water is removed continuously. Mineral oil 
(470 parts) is added and reaction mixture is stripped to 196.degree. C. 
under vacuum. The reaction mixture is filtered at 145.degree. C. to yield 
the desired product (60% solution in mineral oil). 
EXAMPLE 22 
A mixture of 1 mole of poly(isobutene)-substituted phenol (substituent 
Mn=1600 by VPO) and 3 moles of formaldehyde are reacted in mineral oil 
diluent (47.5%) at 30.degree. C. to form the desired intermediate. Then to 
746 parts of this intermediate oil solution and 300 parts of benzene is 
added 27 parts of pentaerythritol. The mixture is heated at 90.degree. to 
150.degree. C. for 1.75 hours and at 150.degree. to 215.degree. C. for an 
additional 1.25 hours. The mixture is held at 215.degree.-220.degree. C. 
for 6 hours and filtered to provide an oil solution of the desired 
product. 
The compositions of this invention can be further modified by sulfurization 
with elemental sulfur. This is accomplished by reacting the composition 
with elemental sulfur at a temperature ranging from the melting point of 
the sulfur being used up to about 300.degree. C. to produce a product 
having about 0.1 to about 20% sulfur by weight. The ratio by weight of 
compositions to sulfur used in these sulfurizations is usually about 
1:0.1-1. These sulfurized products improve the oxidation and thermal 
stability of fuels and lubricants containing them as well as imparting 
sludge-dispersing and detergent properties to the fuel or lubricant. 
EXAMPLES 23, 24 AND 25 
The products of examples 1, 7 and 13 are sulfurized by the same general 
procedure. The oil solutions of each product as obtained (500 parts) are 
mixed with flowers of sulfur (64 parts) and the resultant mixture heated 
at 185.degree. C. for 13 hours. Provision is made for collecting the 
hydrogen sulfide generated by venting the reaction vessel to a caustic 
trap. The reaction mixture is then filtered through diatomaceous earth to 
provide, as a filtrate, an oil solution of the desired sulfurized product. 
As previously indicated, the compositions of this invention are useful as 
additives for lubricants, in which they function primarily as sludge 
dispersants and detergents. Such dispersants and detergents disperse and 
remove from surfaces sludge which forms in the lubricant during use. They 
can be employed in a variety of lubricants based on diverse oils of 
lubricating viscosity, including natural and synthetic lubricating oils 
and mixtures thereof as well as greases derived therefrom. These 
lubricants include crankcase lubricating oils for spark-ignited and 
compression-ignited internal combustion engines, such as automobile and 
truck engines, two-cycle engines, marine and railroad diesel engines, and 
the like. They can also be used in gas engines, stationary power engines 
and turbines and the like. Automatic transmission fluids, transaxle 
lubricants, gear lubricants, metal-working lubricants, hydraulic fluids 
and other lubricating oil and grease compositions can also benefit from 
the incorporation therein of the compositions of the present invention. 
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard 
oil) as well as mineral lubricating oils such as liquid petroleum oils and 
solvent-treated or acid-treated mineral lubricating oils of the 
paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of 
lubricating viscosity derived from coal or shale are also useful base 
oils. Synthetic lubricating oils include hydrocarbon oils and 
halosubstituted hydrocarbon oils such as polymerized and interpolymerized 
olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene 
copolymers, chlorinated polybutylenes, etc.); poly(1-hexenes), 
poly(1-octenes), poly(1-decenes), etc. and mixtures thereof; alkylbenzenes 
(e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, 
di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g., biphenyls, 
terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and 
alkylated diphenyl sulfides and the derivatives, analogs and homologs 
thereof and the like. 
Alkylene oxide polymers and interpolymers and derivatives thereof where the 
terminal hydroxyl groups have been modified by esterification, 
etherification, etc. constitute another class of known synthetic 
lubricating oils. These are exemplified by the oils prepared through 
polymerization of ethylene oxide or propylene oxide, the alkyl and aryl 
ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene 
glycol ether having an average molecular weight of 1000, diphenyl ether of 
polyethylene glycol having a molecular weight of 500-1000, diethyl ether 
of polypropylene glycol having a molecular weight of 1000-1500, etc.) or 
mono- and polycarboxylic esters thereof, for example, the acetic acid 
esters, mixed C.sub.3 -C.sub.8 fatty acid esters, or the C.sub.13 Oxo acid 
diester of tetraethylene glycol. 
Another suitable class of synthetic lubricating oils comprises the esters 
of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic 
acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, 
sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic 
acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of 
alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 
2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, 
propylene glycol, etc.). Specific examples of these esters include dibutyl 
adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, 
diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl 
phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid 
dimer, the complex ester formed by reacting one mole of sebacic acid with 
two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid 
and the like. 
Esters useful as synthetic oils also include those made from C.sub.5 to 
C.sub.12 monocarboxylic acids and polyols and polyol ethers such as 
neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, 
tripentaerythritol, etc. 
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or 
polyaryloxy-siloxane oils and silicate oils comprise another useful class 
of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl 
silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, 
tetra-(p-tert-butylphenyl)silicate, hexyl-(4-methyl-2-pentoxy)disiloxane, 
poly(methyl)siloxanes, poly(methylphenyl)siloxanes, etc.). Other synthetic 
lubricating oils include liquid esters of phosphorus-containing acids 
(e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane 
phosphonic acid, etc.), polymeric tetrahydrofurans and the like. 
Unrefined, refined and rerefined oils, either natural or synthetic (as well 
as mixtures of two or more of any of these) of the type disclosed 
hereinabove can be used in the lubricant compositions of the present 
invention. Unrefined oils are those obtained directly from a natural or 
synthetic source without further purification treatment. For example, a 
shale oil obtained directly from retorting operations, a petroleum oil 
obtained directly from primary distillation or ester oil obtained directly 
from an esterification process and used without further treatment would be 
an unrefined oil. Refined oils are similar to the unrefined oils except 
they have been further treated in one or more purification steps to 
improve one or more properties. Many such purification techniques are 
known to those skilled in the art such as solvent extraction, secondary 
distillation, acid or base extraction, filtration, percolation, etc. 
Rerefined oils are obtained by processes similar to those used to obtain 
refined oils applied to refined oils which have been already used in 
service. Such rerefined oils are also known as reclaimed or reprocessed 
oils and often are additionally processed by techniques directed to 
removal of spent additives and oil breakdown products. 
In general, about 0.05-20.0 parts, usually about 1-10 parts, of the 
compositions of this invention are dissolved or stably dispersed in 100 
parts of oil to produce a satisfactory lubricant. The invention also 
contemplates the use of other additives in combination with the 
composition of this invention. Such additives include, for example, 
auxiliary detergents and dispersants of the ash-producing or ashless type, 
oxidation inhibiting agents, pour point depressing agents, extreme 
pressure agents, color stabilizers and anti-foam agents. 
The ash-producing detergents are exemplified by oil-soluble neutral and 
basic salts of alkali or alkaline earth metals with sulfonic acids, 
carboxylic acids, or organic phosphorus acids chracterized by at least one 
direct carbon-to-phosphorus linkage such as those prepared by the 
treatment of an olefin polymer (e.g., polyisobutene having a molecular 
weight of 1000) with a phosphorizing agent such as phosphorus trichloride, 
phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride 
and sulfur, white phosphorus and a sulfur halide, or phosphorothioic 
chloride. The most commonly used salts of such acids are those of sodium, 
potassium, lithium, calcium, magnesium, strontium and barium. 
The term "basic salt" is used to designate metal salts wherein the metal is 
present in stoichiometrically larger amounts than the organic acid 
radical. The commonly employed methods for preparing the basic salts 
involve heating a mineral oil solution of an acid with a stoichiometric 
excess of a metal neutralizing agent such as the metal oxide, hydroxide, 
carbonate, bicarbonate, or sulfide at a temperature above 50.degree. C. 
and filtering the resulting mass. The use of a "promoter" in the 
neutralization step to aid the incorporation of a large excess of metal 
likewise is known. Examples of compounds useful as the promoter include 
phenolic substances such as phenol, naphthol, C.sub.6-26 alkylphenols, 
thiophenol, sulfurized alkylphenol, and condensation products of 
formaldehyde with a phenolic substance; C.sub.1-20 alcohols such as 
methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene 
glycol, stearyl alcohol, and cyclohexyl alcohol; and C.sub.1-20 amines 
such as aniline, phenylenediamine, phenothiazine, 
phenyl-.beta.-naphthylamine, and dodecylamine. A particularly effective 
method for preparing the basic salts comprises mixing an acid with an 
excess of a basic alkaline earth metal neutralizing agent and at least one 
alcohol promoter, and carbonating the mixture at an elevated temperature 
such as 60.degree.-200.degree. C. 
Ashless detergents and dispersants are so called despite the fact that, 
depending on its constitution, the dispersant may upon combustion yield a 
non-volatile material such as boric oxide or phosphorus pentoxide; 
however, it does not ordinarily contain metal and therefore does not yield 
a metal-containing ash on combustion. Many types are known in the art, and 
any of them are suitable for use in the lubricants of this invention. The 
following are illustrative: 
(1) Reaction products of carboxylic acids (or derivatives thereof) 
containing at least about 34 and preferably at least about 54 carbon atoms 
with nitrogen-containing compounds such as amines, organic hydroxy 
compounds such as phenols and alcohols, and/or basic inorganic materials. 
Examples of these "carboxylic dispersants" are described in British Pat. 
No. 1,306,529 and in many U.S. Patents, including the following: 
______________________________________ 
3,163,603 3,351,552 3,541,012 
3,184,474 3,381,022 3,542,678 
3,215,707 3,399,141 3,542,680 
3,219,666 3,415,750 3,567,637 
3,271,310 3,433,744 3,574,101 
3,272,746 3,444,170 3,576,743 
3,281,357 3,448,048 3,630,904 
3,306,908 3,448,049 3,632,510 
3,311,558 3,451,933 3,632,511 
3,316,177 3,454,607 3,697,428 
3,340,281 3,467,668 3,725,441 
3,341,542 3,501,405 Re 26,433 
3,346,493 3,522,179 
______________________________________ 
(2) Reaction products of relatively high molecular weight aliphatic or 
alicyclic halides with amines, preferably polyalkylene polyamines. These 
may be characterized as "amine dispersants" and examples thereof are 
described, for example, in the following U.S. Patents: 
______________________________________ 
3,275,554 3,454,555 
3,438,757 3,565,804 
______________________________________ 
(3) Products obtained by post-treating the carboxylic or amine dispersants 
with such reagents as urea, thiourea, carbon disulfide, aldehydes, 
ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, 
nitriles, epoxides, boron compounds, phosphorus compounds or the like. 
Exemplary materials of this kind are described in the following U.S. 
Patents: 
______________________________________ 
3,036,003 3,367,943 3,579,450 
3,087,936 3,373,111 3,591,598 
3,200,107 3,403,102 3,600,372 
3,216,936 3,442,808 3,639,242 
3,254,025 3,455,831 3,649,229 
3,256,185 3,455,832 3,649,659 
3,278,550 3,493,520 3,658,836 
3,280,234 3,502,677 3,697,574 
3,281,428 3,513,093 3,702,757 
3,282,955 3,533,945 3,703,536 
3,312,619 3,539,633 3,704,308 
3,366,569 3,573,010 3,708,522 
______________________________________ 
(4) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, 
vinyl decyl ether and high molecular weight olefins with monomers 
containing polar substituents, e.g., aminoalkyl acrylates or acrylamides 
and poly-(oxyethylene)-substituted acrylates. These may be characterized 
as "polymeric dispersants" and examples thereof are disclosed in the 
following U.S. Patents: 
______________________________________ 
3,329,658 3,666,730 
3,449,250 3,687,849 
3,519,565 3,702,300 
______________________________________ 
The pertinent disclosures of all of the above-noted patents are 
incorporated by reference herein. 
Extreme pressure agents and corrosion-inhibiting and oxidation-inhibiting 
agents are exemplified by chlorinated aliphatic hydrocarbons such as 
chlorinated wax; organic sulfides and polysulfides such as benzyl 
disulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized 
methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, 
and sulfurized terpene; phosphosulfurized hydrocarbons such as the 
reaction product of a phosphorus sulfide with turpentine or methyl oleate; 
phosphorus esters including principally dihydrocarbon and trihydrocarbon 
phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl 
phosphite, pentyl phenyl phosphite, dipentyl phenyl phosphite, tridecyl 
phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 
4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted 
phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal 
thiocarbamates, such as zinc dioctyldithiocarbamate, and barium 
heptylphenyl dithiocarbamate; Group II metal phosphorodithioates such as 
zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, 
barium di(heptylphenyl)-phosphorodithioate, cadmium 
dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid 
produced by the reaction of phosphorus pentasulfide with an equimolar 
mixture of isopropyl alcohol and n-hexanol. 
The fuel compositions of the present invention contain a major proportion 
of a normally liquid fuel, usually a hydrocarbonaceous petroleum 
distillate fuel such as motor gasoline as defined by ASTM Specification 
D-439-73 and diesel fuel or fuel oil as defined by ASTM Specification 
D-396. Normally liquid fuel compositions comprising non-hydrocarbonaceous 
materials such as alcohols, ethers, organo-nitro compounds and the like 
(e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) 
are also within the scope of this invention as are liquid fuels derived 
from vegetable or mineral sources such as corn, alfalfa, shale and coal. 
Normally liquid fuels which are mixtures of one or more hydrocarbonaceous 
fuels and one or more non-hydrocarbonaceous materials are also 
contemplated. Examples of such mixtures are combinations of gasoline and 
ethanol, diesel fuel and ether, gasoline and nitromethane, etc. 
Particularly preferred is gasoline, that is, a mixture of hydrocarbons 
having an ASTM boiling point of 60.degree. C. at the 10% distillation 
point to about 205.degree. C. at the 90% distillation point. 
Generally, these fuel compositions contain an amount of the compositions of 
this invention sufficient to impart dispersant and detergent properties to 
the fuel; usually this amount is about 1 to about 10,000 preferably 4 to 
1,000 parts by weight of the reaction product per million parts by weight 
of fuel. The preferred gasoline-based fuel compositions generally exhibit 
excellent engine sludge dispersancy and detergency properties. In 
addition, they exhibit anti-rust and carburetor/fuel line deposit-removing 
and deposit-inhibiting properties. 
The fuel compositions of this invention can contain, in addition to the 
compositions of this invention, other additives which are well known to 
those of skill in the art. These can include anti-knock agents such as 
tetra-alkyl lead compounds, lead scavengers such as halo-alkanes (e.g., 
ethylene dichloride and ethylene dibromide), deposit preventors or 
modifiers such as triaryl phosphates, dyes, cetane improvers, 
anti-oxidants such as 2,6-di-tertiarybutyl-4-methylphenol, rust 
inhibitors, such as alkylated succinic acids and anhydrides, 
bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, 
upper cylinder lubricants, anti-icing agents and the like. 
In certain preferred fuel compositions of the present invention, the 
afore-described compositions of this invention are combined with other 
ashless dispersants in gasoline. Such ashless dispersants are preferably 
esters of a mono- or polyol and a high molecular weight mono- or 
polycarboxylic acid acylating agent containing at least 30 carbon atoms in 
the acyl moiety. Such esters are well known to those of skill in the art. 
See, for example, French Pat. No. 1,396,645, British Pat. Nos. 981,850 and 
1,055,337 and U.S. Pat. Nos. 3,255,108; 3,311,558; 3,331,776; 3,346,354; 
3,522,179; 3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428; 
3,708,522; and British Patent Specification No. 1,306,529. These patents 
are expressly incorporated herein by reference for their disclosure of 
suitable esters and methods for their preparation. Generally, the weight 
ratio of the compositions of this invention to the aforesaid ashless 
dispersants is about 0.1 to about 10.0; preferably about 1 to about 10 
parts of composition of this invention to 1 part ashless dispersant. 
In still another embodiment of this invention, the inventive additives for 
fuels and lubricants are combined with Mannich condensation products 
formed from substituted phenols, aldehydes, polyamines, and amino 
pyridines. Such condensation products are described in U.S. Pat. Nos. 
3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,725,277. 
The compositions of this invention can be added directly to the fuel or 
lubricating oil to form the fuel and lubricant compositions of this 
invention or they can be diluted with a substantially inert, normally 
liquid organic solvent/diluent such as mineral oil, xylene, or a normally 
liquid fuel as described above, to form an additive concentrate which is 
then added to the fuel or lubricating oil in sufficient amounts to form 
the inventive fuel and lubricant composition described herein. These 
concentrates generally contain about 10-90, usually 20-80 percent of the 
composition of this invention and can contain in addition any of the 
above-described conventional additives, particularly the afore-described 
ashless dispersants including Mannich condensates in the aforesaid 
proportions. The remainder of the concentrate is the solvent/diluent.