U.S. patent number 3,803,039 [Application Number 05/231,030] was granted by the patent office on 1974-04-09 for oil solution of aliphatic acid derivatives of high molecular weight mannich condensation product.
This patent grant is currently assigned to Standard Oil Company. Invention is credited to Robert E. Karll, Edmund J. Piasek.
United States Patent |
3,803,039 |
Piasek , et al. |
April 9, 1974 |
OIL SOLUTION OF ALIPHATIC ACID DERIVATIVES OF HIGH MOLECULAR WEIGHT
MANNICH CONDENSATION PRODUCT
Abstract
Protection against corrosion and deposition of sludge and
varnish is provided by lubricating oils containing a minor amount
of the ashless addition agents which are aliphatic acid derivatives
of high molecular weight Mannich condensation products of (1) high
molecular weight alkyl-substituted hydroxy aromatic compounds whose
alkyl-substituent has a number average molecular weight (Mn) from
about 600-100,000, (2) a compound containing at least one ##SPC1##
Group, (3) an aldehyde in the respective molar reactant ratio of
1:0.1-10:1.0-10, and (4) 0.1-10.0 weight percent of an aliphatic
acid having at least 6 carbon atoms.
Inventors: |
Piasek; Edmund J. (Chicago,
IL), Karll; Robert E. (Batavia, IL) |
Assignee: |
Standard Oil Company (Chicago,
IL)
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Family
ID: |
26733176 |
Appl.
No.: |
05/231,030 |
Filed: |
March 1, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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54558 |
Jul 13, 1970 |
3641799 |
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Current U.S.
Class: |
508/453;
528/162 |
Current CPC
Class: |
C08F
110/00 (20130101); C08F 8/32 (20130101); C10M
1/08 (20130101); C08F 8/32 (20130101); C10M
2209/084 (20130101); C10M 2215/12 (20130101); C10M
2217/043 (20130101); C10M 2229/05 (20130101); C10M
2215/22 (20130101); C10M 2215/221 (20130101); C10M
2229/02 (20130101); C10M 2215/225 (20130101); C10M
2215/30 (20130101); C10M 2217/046 (20130101); C10M
2217/06 (20130101); C10N 2010/04 (20130101); C10M
2207/34 (20130101); C10M 2215/062 (20130101); C10N
2040/04 (20130101); C10M 2219/044 (20130101); C10M
2205/02 (20130101); C10M 2205/028 (20130101); C10M
2203/06 (20130101); C10N 2040/042 (20200501); C10M
2215/224 (20130101); C10N 2040/046 (20200501); C10M
2207/282 (20130101); C10M 2223/045 (20130101); C10M
2215/08 (20130101); C10M 2217/042 (20130101); C10N
2040/044 (20200501); C10M 2205/00 (20130101); C10M
2215/26 (20130101); C10M 2205/026 (20130101); C10M
2215/082 (20130101); C10M 2217/028 (20130101); C10M
2209/103 (20130101); C10M 2215/226 (20130101); C10M
2215/04 (20130101); C10M 2215/28 (20130101) |
Current International
Class: |
C08F
8/00 (20060101); C08F 8/32 (20060101); C10m
001/32 () |
Field of
Search: |
;252/51.5A |
References Cited
[Referenced By]
U.S. Patent Documents
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3493520 |
February 1970 |
Verdol et al. |
|
Primary Examiner: Bellamy; Werten F. W.
Attorney, Agent or Firm: Ahlers; Fred R. Gilkes; Arthur G.
McClain; William T.
Parent Case Text
RELATED APPLICATION
This application is a division of copending application Ser. No.
54,558, filed July 13, 1970 which is now U.S. Pat. No. 3,641,799.
Claims
1. A lubricant oil composition comprising a major amount of a
normally liquid oleaginous lubricant and a minor
detergent-dispersant amount of an oil-soluble aliphatic acid
modified high molecular weight product of the Mannich Reaction
conducted at a temperature of from about 300.degree. F. to about
375.degree. F., with:
a. a high molecular weight alkyl-substituted hydroxyaromatic
compound wherein the alkyl substituent has an average molecular
weight of from about 600 to about 100,000;
b. an amine containing at least one ##SPC20##
group;
c. an aliphatic aldehyde; and
d. saturated or unsaturated aliphatic monocarboxylic acid
containing from six to 30 carbon atoms or polymers of such
unsaturated acid wherein said reactants are used in the respective
reactant molar ratio of
2. The lubricant oil composition of claim 1 wherein said minor
detergent-dispersant amount is in the range of 0.05 to 10 weight
percent.
3. The lubricant oil composition of claim 2, wherein the high
molecular weight alkyl-substituted hydroxyaromatic compound is a
polyalkyl-substituted phenol, wherein the polyalkyl substituent has
a
4. The lubricant oil composition of claim 2, wherein the amine is
selected from the group consisting of polyalkylpolyamines and
polyalkenepolyamines.
5. The lubricant oil composition of claim 2, wherein the amine is
selected from the group consisting of tetraethylene pentamine and
diethylene
6. The lubricant oil composition of claim 2, wherein the aldehyde
is selected from the group consisting of formaldehyde and
paraformaldehyde.
7. The lubricant oil composition of claim 2, wherein the aliphatic
acid is
8. The lubricant oil composition of claim 2 wherein the reactants
are:
a. polybutyl-substituted phenol in which the polybutyl-substituent
has an average molecular weight of from about 600 to about
3,000;
b. ethylene polyamine;
c. formaldehyde affording reactant; and
d. oleic acid and wherein said reactants are used in the
respective
9. The lubricant oil composition of claim 8 wherein the
polybutyl-substituent has a molecular weight of about 1,500, the
ethylene polyamine is tetraethylene pentamine and the formaldehyde
affording
10. The lubricant oil composition of claim 9 wherein the normally
liquid oleaginous lubricant is a mineral lubricating oil.
Description
BACKGROUND OF THE INVENTION
This invention relates to improved lubricating oils and
particularly concerns automobile and Diesel crankcase lubricating
oil formulations containing a minor amount of a new class of
oil-soluble addition agents which improve the performance of the
oil, particularly its dispersant-detergent function thus enabling
lubricating oils to provide a high degree of protection of the
lubricated parts of internal combustion engines.
Present-day automobile and Diesel engines have been designed for
higher power output, lower combustion products emission and longer
in-service periods of use of crankcase lubricating oils. These
design changes have resulted in such severe operating conditions as
to necessitate devising higher efficiency lubricating oils that
will, under the increased severity of in-service use, afford proper
protection against corrosion and the accumulation or deposition of
sludge, varnish and resinous materials on the surface of engine
parts which rapidly accelerate decrease in both operating
efficiency and life of the engine. The principal ingredient of
crankcase lubricants is a base lubricating oil, a mixture of
hydrocarbons derived from petroleum. Even when highly refined by
removal of deleterious components, such as polymerizable
components, acid formers, waxes, etc., a lubricant base oil still
requires the addition of a number of oil-soluble chemical additives
to enable the oil to resist oxidation, deposition of sludge and
varnish on, and corrosion of, the lubricated metal parts, and to
provide added lubricity and regulated viscosity change from low to
high temperature. These ingredients are commonly known as
anti-oxidants, dispersant-detergents, pour point dispersants,
etc.
Combustion products from the burning of fuel and thermal
degradation of lubricating oils and addition agents tend to
concentrate in the crankcase oil with the attendant formation of
oil-insoluble deposit-forming products, that either surface coat
the engine parts (varnish or lacquer-like films) or settle out on
the engine parts as viscous (sludge) deposits or form solid
ash-like or carbonaceous deposits. Any of such deposits can
restrict, and even plug, grooves, channels and holes provided for
lubricant flow to the moving surfaces of the engine requiring
lubrication thus accelerating the wear and thus reducing the
efficiency of the engine. In addition, acidic combustion products
corrode the lubricated metal surfaces. Chemical additives are
blended in crankcase oil formulations not only to reduce thermal
decomposition of the oil and addition agents (anti-oxidants) but
also to keep in suspension (as a dispersant) and to resuspend (as a
detergent) insoluble combustion and degradation products as well as
to neutralize acidic products (anti-corrosion agents). A separate
additive is usually added for each improvement to be effected.
Various ingredients have been developed for the purpose of
providing the dispersant-detergent function. Neutral and overbased
metallo-organic compounds, such as the alkaline earth metal salts
of sulfonic acids and hydrocarbon-P.sub.2 S.sub.5 reaction products
were the first addition agents used for this purpose. Their
in-service drawbacks included the formation of metal-ash thermal
decomposition products which deposited on engine parts; they could
not efficiently disperse or resuspend lacquer or varnish formers or
sludge formers; and they lost their dispersant-detergent function
when their alkaline earth metal component had been consumed in
neutralizing acidic products of combustion.
As performance levels increased and the recommended periods between
oil drains lengthened for both automobile and railway Diesel
engines, more efficient dispersancy and detergency performance as
well as acid neutralization and lower ash-forming tendency were
demanded for lubricating oil formulations. During the past several
years, a great deal of time and effort has been directed at
providing addition agents for lubricants capable of satisfying such
performance demands. When high molecular weight polybutene polymers
became commercially available in the early 1940's, research workers
in various laboratories devised, for this dispersant-detergent
function, a series of derivatives of polybutene-phosphorus
pentasulfide reaction products, e.g. alkaline earth metal salts,
alkylene polyamine and alkylene oxide derivatives, in which the
high molecular weight of the polybutene group greatly enhanced
their effectiveness. Others devised amine salts, amides, imides and
amidines of polybutenyl-substituted polycarboxylic acids and
polymeric compounds having pendant or grafted-on polar groups.
Still others suggested combinations of alkaline earth metal
sulfonates and Mannich condensation products of a low molecular
weight alkyl (C.sub.2 -C.sub.20) substituted hydroxyaromatic
compound, an amine having at least one replaceable hydrogen on a
nitrogen and an aldehyde and alkaline earth metal salts (phenates)
of those Mannich condensation products but without notable success.
The later compositions still possessed the objectionable feature of
forming harmful metal-ash deposits, and were incapable of providing
the increased dispersancy-detergency service demanded for long
drain service of present-day engine requirements.
Mannich condensation products derived from alkyl-substituted
hydroxyaromatic compounds having a relatively low molecular weight
alkyl substituent, i.e., 2 to 20 carbon atoms in the alkyl
substituent and chlorinated wax (straight chain) type
alkyl-substituents are described in U.S. Pat. Nos. 2,403,453;
2,353,491; 2,363,134; 2,459,112; 2,984,550 and 3,036,003. However,
none of such prior Mannich condensation products are suitable for
use as dispersant-detergent addition agents for present-day long
drain oil interval in-service use.
One known type (U.S. Pat. No. 2,363,134) has been prepared by
reacting, under Mannich reaction conditions, equimolar quantities
of a C.sub.2 -C.sub.20 alkyl-substituted phenol and other hydroxy
aromatic compounds, and N,N-di-substituted amine and formaldehyde
according to the following equation: ##SPC2##
wherein R is an alkyl group having between 2 and 20 carbon atoms
and R.sub.1 and R.sub.2 may be alkyl, cycloalkyl, aryl or arakyl
radicals.
Other prior low molecular weight Mannich condensation products
formed by condensing a C.sub.2 to C.sub.20 alkyl-substituted
phenol, an alkylene diamine and an aldehyde in the respective molar
ratios of 2:1:2, have been illustrated by the following structural
formula: ##SPC3##
wherein R is a divalent alkylene hydrocarbon radical and R.sub.1 is
an alkyl group containing from 2 to 20 carbon atoms.
Still others have been prepared by reacting C.sub.2 -C.sub.20
alkylphenols, formaldehyde and alkylene polyamines of the formula
##SPC4##
wherein A is a divalent alkylene radical of 2 to 6 carbon atoms and
n is an integer from 1 to 10, in the ratio of from 0.5 to 2 moles
each of C.sub.2 -C.sub.20 alkylphenol and formaldehyde for each
nitrogen group contained in the alkylene polyamine reagent. The
molar reactant ratio range of C.sub.2 -C.sub.20 alkylphenol, amine
and formaldehyde used to form such products is 1-20:1.0:1-20. U.S.
Pat. No. 3,036,003 exemplifies such products, which usually are
formed with ethylene polyamines, according to the above formula in
which A is -CH.sub.2 -CH.sub.2 - and n is 2, 3 and 4.
The foregoing prior C.sub.2 -C.sub.20 alkyl-substituted Mannich
condensation products commonly are prepared by the conventional
technique of adding the aliphatic aldehyde to a heated mixture of
the alkylhydroxyaromatic and amine reagents, in the presence or
absence of a solvent, and then heating the resultant mixture to a
temperature between 100.degree.-350.degree. F. until dehydration is
complete. A solvent such as benzene, toluene, xylene, methanol and
others easily separated from the reaction mixture are light
minerals oils, such as those used in blending stocks to prepare
lubricating oil formulations in which the product is formed as a
mineral oil concentrate are usually used. The water by-product is
removed by heating the reaction mixture to a temperature
sufficiently high, at least during the last part of the process, to
drive off the water alone, or as an azeotropic mixture with the
aromatic solvent, usually by the aid of an inert stripping gas,
such as nitrogen, carbon dioxide, etc.
The exactly neutralized or overbased alkaline earth metal salts
(alkaline earth metal phenates) of those prior low molecular weight
Mannich condensation products have been suggested for use in
providing lubricating oils with a combination of
detergent-inhibitor properties in one addition agent. The exactly
neutralized alkaline earth metal salts have one equivalent of
alkaline earth metal for each hydroxy group present. The overbased
salts have, for each hydroxy group present, more than one
equivalent of alkaline earth metal in the form of a hydroxy
metaloxy, alkoxy metaloxy and even alkaline earth metal carbonate
complex with hydroxy metaloxy on each benzene group as a
replacement for the phenol hydroxy group. As noted above, said
addition agents form objectionable metal ash deposits and have
other performance deficiencies.
U.S. Pat. No. 3,235,484 issued Feb. 15, 1966 (Now U.S. Pat. Reissue
No. 26,330) describes the addition agents of certain disclosed
compositions to refinery hydrocarbon feed stocks for the purpose of
inhibiting the accumulation of carbonaceous deposits in refinery
cracking units. The primary inhibitors disclosed are mixtures of
amides, imides and amine salt formed by reacting an ethylene
polyamine with hydrocarbon substituted succinic acids or anhydride,
whose hydrocarbon substituent has at least about 50 carbon atoms.
As an adjunct for such primary carbonaceous deposit inhibitors
there is disclosed in said patent Mannich condensation products
formed by reacting (1) alkylphenol, (2) an amine and (3)
formaldehyde in the ratio of one mole alkylphenol and from 0.1-10
mole formaldehyde for each active nitrogen group contained in the
amine reactant. Alkylphenols whose alkyl group has a molecular
weight as high as 50,000 and contains from monoalkylphenols whose
alkyl group contains 4-30 carbon atoms are stated to be the
preferred alkylphenol reactants.
U.S. Pat. No. 3,368,972 issued Feb. 13, 1968 describes as
dispersant-detergent addition agents for lubricating oils high
molecular weight Mannich condensation products from (1) high
molecular weight alkyl-substituted hydroxyaromatic compounds whose
alkyl-substituent has a molecular weight in the range of 600-3,000,
(2) a compound containing at least one ##SPC5##
group and (3) an aldehyde in the respective molar ratio of
1.0:0.1-10:1.0-10.
Said high molecular weight Mannich condensation products of either
U.S. Pat. No. 3,235,484 or U.S. Pat. No. 3,368,972 have a drawback
in their large-scale preparation and in their extended service use
as lubricant addition agents used under high temperature conditions
such as encountered in diesel engines. In the large-scale or plant
preparation of such high molecular weight condensation products,
especially in light mineral oil solvents, the resulting oil
concentrate solution of the condensation product either has or
develops during storage a haze which is believed to be caused by
undissolved or borderline soluble by-products which not only are
not only substantially incapable of removal by filtration but also
severely restrict product filtration rate. When used in diesel
engine crankcase lubricant oils and subject to high temperature in
service use, piston ring groove carbonaceous deposits and skirt
varnish tend to build up sufficiently rapidly and prevent desirable
long in-service use of such lubricant oils.
We have discovered that both of those drawbacks can be overcome by
the use of an aliphatic acid having suitably from about 6 carbon
atoms to about 30 carbon atoms, desirably at least 10 carbon atoms
and preferably 16 or more carbon atoms per carboxylic acid group.
The aliphatic acid can be used as an initial reactant, reacted with
the hazy high molecular weight Mannich condensation product before
its filtration or added to the filtered product before it goes to
storage. Such uses of the aliphatic acid require only small
amounts, in the range of 0.1-10.0 weight percent to eliminate those
drawbacks and provide an improved product.
BRIEF SUMMARY OF THE INVENTION
This invention pertains to lubricant oil compositions comprising a
major amount of lubricating oil and a minor amount, 0.05 to 10
weight percent, of a new class of compounds useful as
multifunctional addition agents for lubricating oils, particularly
such oils used in internal combustion engines in which they
function as highly efficient dispersant-detergent and oxidation
inhibitor agents.
The new class of compounds which comprise the addition agent
component of this invention are oil-soluble high molecular
aliphatic acid modified weight products of the Mannich Reaction.
They can be prepared either by condensing in the usual manner under
conditions of the Mannich Reaction:
1. an alkyl-substituted hydroxyaromatic compound, whose
alkyl-substituent has a 600-100,000 Mn, preferably a
polyalkylphenol whose polyalkyl substituent is derived from
1-mono-olefin polymers having a Mn of about 850-2,500;
2. an amine containing at least one ##SPC6## group, preferably an
alkylene polyamine of the formula ##SPC7##
wherein A is a divalent alkylene radical having 2 to 6 carbon atoms
and x is an integer from 1 to 10; and
3. an aldehyde, preferably formaldehyde followed by reaction with
(4) aliphatic acid before or after filtration. Or they can be
prepared by using all four reactants at one time under the general
Mannich reaction conditions.
The foregoing high molecular weight products of this invention are
preferably prepared according to the conventional methods
heretofore employed for the preparation of Mannich Reaction
condensation products, using the above-named reactants in the
respective molar ratios of high molecular weight alkyl-substituted
hydroxyaromatic compound, amine, aldehyde and aliphatic acid of
approximately 1.0:0.1-10:1.0-10:0.014-1.0. Suitable as a
condensation procedure involves adding at a temperature of from
room temperatures to about 200.degree. F. the formaldehyde reagent
(e.g. formalin) to a mixture of reagents (1), (2) and (4) above or
in an easily removed organic solvent, such as benzene, xylene or
toluene or in solvent refined neutral oil and then heating the
reaction at an elevated temperature (275.degree.-375.degree. F.)
preferably flowing with an inert stripping gas, such as nitrogen,
carbon dioxide, etc. until dehydration is complete.
The preferred additives according to this invention are high
molecular weight bis-Mannich condensation products formed by
reacting (1) a 850-2,500 Mn polyalkylphenol; (2) an ethylene
polyamine, as amine reactant; (3) formaldehyde and (4) an aliphatic
acid in the respective molar ratio of
1.0:0.7-1.0:1.5-2.1:0.014-0.62.
The novel addition agents according to our invention are the high
molecular weight aliphatic acid modified Mannich Reaction
condensation products of (1) high molecular weight
alkyl-substituted phenol whose alkyl substituent has a Mn of
600-100,000, a compound having at least one ##SPC8##
group, an aldehyde and an aliphatic acid wherein the respective
molar ratio of the reactants is 1.0:0.1-10:1.0-10:0.014-0.62.
Preferred addition agents are those obtained by condensing (1) an
alkylphenol whose alkyl substituent is derived from 1-mono-olefin
polymers having a 850-2,500 Mn; (2) an alkylene polyamine having
the formula H.sub.2 N-(A-NH).sub.n H wherein A is a divalent
saturated hydrocarbon radical having 2 to 6 carbon atoms and n is
an integer from 1 to 10, (3) a formaldehyde yielding reactant and
(4) an aliphatic acid having 10-20 carbon atoms per carboxylic acid
group used in the respective molar ratio of reactants is
1:0.7-1.0:1.5-2.1:0.014-0.62.
The high molecular weight products of this invention are
exceptionally useful addition agents for lubricating oils imparting
thereto dispersant-detergent and anti-oxidant properties at
relatively low concentrations of the addition agent, e.g., 0.05 to
10 weight percent in formulated crankcase lubricating oil. Higher
concentrations, e.g., 10 to 70 weight percent, are useful
concentrates of the preparation of those formulated crankcase
lubrication oils and the fortification of crankcase oil in use
prior to the scheduled complete drain. For a more complete
understanding of the Mannich Reaction see "Organic Reactions," Vol.
1 pages 303 to 341 (1942) published by John Wiley & Sons,
Inc.
Representative lubricating oils for the lubricant oil compositions
of this invention include the normally liquid oleaginous lubricants
which are hydrocarbon fractions derived from petroleum and
synthetic ester or alkylene oxide type lubricants having the
viscosity within the range represented by SAE 5 to SAE 50 weight
mineral oils. Such lubricating oils can be single oils within said
viscosity range or mixtures of such oils as well as mixtures of
such mineral oils with a synthetic type lubricant. For use in
automobile and diesel engines it is preferred that the lubricant
oil compositions contain a major amount of said mineral oil derived
from petroleum and said mineral oil can be a petroleum fraction or
the hydrogenated derivative thereof. There can also be present and
preferably is present when more than one viscosity lubricant
comprises the lubricant oil major portion, a viscosity index (VI)
improver such as the rather viscous, oily polybutene VI improver
and/or the polyacrylate type VI improver.
EMBODIMENTS OF THE INVENTION
Representative high molecular weight aliphatic acid modified
Mannich condensation products contemplated by this invention can be
prepared from the following representative reactants of the classes
before defined.
1. High Molecular Weight Alkyl-Substituted Hydroxyaromatics
Representative of these high molecular weight alkyl-substituted
hydroxyaromatic compounds are polypropylphenol, polybutylphenol and
other polyalkylphenols. These polyalkylphenols may be obtained by
the alkylation, in the presence of an alkylating catalyst, such as
BF.sub.3, of phenol with high molecular weight polypropylene,
polybutylene and other polyalkylene compounds to give alkyl
substituents on the benzene ring of phenol having an average
600-100,000 Mn. Their preparations using a BF.sub.3 phenol catalyst
is described and claimed in our copending application Ser. No.
484,758, filed Sept. 2, 1965.
The 600 Mn and higher Mn alkyl-substituents on the hydroxyaromatic
compounds may be derived from high molecular weight polypropylenes,
polybutenes and other polymers of mono-olefins, principally
1-mono-olefins. Also useful are copolymers of mono-olefins with
monomers copolymerizable therewith wherein the copolymer molecule
contains at least 90%, by weight, of mono-olefin units. Specific
examples are copolymers of butenes (butene-1, butene-2 and
isobutylene) with monomers copolymerizable therewith wherein the
copolymer molecule contains at least 90%, by weight, of propylene
and butene units, respectively. Said monomers copolymerizable with
propylene or said butenes include monomers containing a small
proportion of unreactive polar groups such as chloro, bromo, keto,
ethereal, aldehyde, which do appreciably lower the oil-solubility
of the polymer. The comonomers polymerized with propylene or said
butenes may be aliphatic and can also contain non-aliphatic groups,
e.g., styrene, methylstyrene, p-dimethylstyrene, divinyl benzene
and the like. From the foregoing limitation placed on the monomer
copolymerized with propylene or said butenes, it is abundantly
clear that said polymers and copolymers of propylene and said
butenes are substantially aliphatic hydrocarbon polymers. Thus the
resulting alkylated phenols contain substantially alkyl hydrocarbon
substituents having Mn upward from 600.
In addition to these high molecular weight hydroxyaromatic
compounds others which may be used include those which have been
used to prepare prior low molecular weight Mannich condensation
products, e.g., high molecular weight alkyl-substituted derivatives
of resorcinol, hydroquinone, cresol, catechol, xylenol, hydroxy
diphenyl, benzylphenol, phenethylphenol, naphthol, tolylnaphthol,
among others. Preferred for the preparation of the before mentioned
preferred bis Mannich condensation products are the polyalkylphenol
reactants, e.g., polypropylphenol and polybutylphenol whose alkyl
group has an average number molecular weight of 600-3,000, the most
preferred being polybutylphenol whose alkyl group has an average
number molecular weight of 850-2,500.
2. ##SPC9## GROUP CONTAINING REACTANTS
Representative of this class of reactants are alkylene polyamines,
principally polyethylene polyamines. Other representative oraganic
compounds containing at least one ##SPC10## group suitable for use
in the preparation of Mannich condensation products are well known
and include the mono and di-amino alkanes and their substituted
analogs, e.g., ethylamine and diethanol amine; aromatic diamines,
e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines,
e.g., morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine,
and piperidine; melamine and their substituted analogs,
Suitable alkylene polyamine reactants include ethylendiamine,
diethylene triamine, triethylene tetramine, tetraethylene
pentamine, pentaethylene hexamine, hexaethylene hapta-amine,
heptaethylene octamine, octaethylene nonamine, nonaethylene
decamine and decaethylene undecamine and mixture of such amines
having nitrogen contents corresponding to the alkylene polyamines,
in the formula H.sub.2 N-(A-NH-).sub.n H, mentioned before, A is
divalent ethylene and n is 1 to 10 of the foregoing formula.
Corresponding propylene polyamines such as propylene diamine and
di-, tri-, tetra-, penta-propylene tri-, tetra-, penta- and
hexa-amines are also suitable reactants. The alkylene polyamines
are usually obtained by the reaction of ammonia and dihalo alkanes,
such as dichloro alkanes. Thus the alkylene polyamines obtained
from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of
dichloro alkanes having 2 to 6 carbon atoms and the chlorines on
different carbons are suitable alkylene polyamine reactants.
ALDEHYDE REACTANTS
Representative of this aldehyde class of reactants for use in the
preparation of the high molecular products of this invention
include the aliphatic aldehydes such as formaldehyde (also as
paraformaldehyde and formalin), acetaldehyde and aldol
(b-hydroxybutyraldehyde). We prefer to use formaldehyde or a
formaldehyde yielding reactants.
ALIPHATIC ACID REACTANTS
The aliphatic acid reactant of this invention has a carbon atom
content of a total (including the carbon of the carboxylic acid
group) of from about six to about 30 and consists of the alkanoic
(saturated) and alkenoic (mono-unsaturated) acids. The upper limit
of the carbon content is restricted only by the largest carbon atom
content of such acids available or capable of feasible preparation.
Such aliphatic acids can be natural and synthetic mono-, di- and
tri-carboxylic acids. Suitable natural aliphatic acids are the
natural fatty acids obtainable by known hydrolysis (acid and
alkaline) of vegetable and animal oils and fats and wax esters. Of
those natural acids for the purposes of this invention the
preferred acids have from 10 to about 20 total carbon atoms per
carboxylic acid group. Suitable synthetic acids can be derived from
oxidation of the alcohol moiety of the wax ester where such alcohol
moiety has at least six carbon atoms; from the polymerization of
unsaturated natural acids having two or three carbon to carbon
double bonds (dimer and trimer acids) and the hydrogenation of
residual carbon to carbon double bonds in such polymer acids. For
example the polymer acids obtained from oleic acid, euric acid,
linoleic acid and linolenic acid and other unsaturated acids; and
from oxidation or other reactions of polypropenes and polybutenes
(e.g. polyisobutenes) which introduce one or more carboxylic acid
group on the polymer chain.
It might be expected that the high molecular weight Mannich product
modified by an unsaturated aliphatic carboxylic acid such as oleic
acid or its C.sub.16 unsaturated homolog would have less oxidation
stability than for example such Mannich products modified by a
saturated aliphatic acid such as stearic acid. But this, somewhat
unexpectedly, is not the case. For example, in a standard oxidation
stability test (Union Pacific Oxidation Test) there are tested oil
formulations containing equivalent amounts of high molecular weight
Mannich Product (a polybutyl-, hydroxybenzyl-substituted
tetraethylene pentamine having a number average molecular weight of
3,600) and the same Mannich Product modified with 0.125 mole (0.8
weight percent) of each of oleic acid, isostearic acid, a mixture
of C.sub.16 and C.sub.18 monounsaturated alkenoic acids and a
mixture of C.sub.16 and C.sub.18 saturated alkanoic acids. The
pentane insolubles content of these tests, indicative of oxidation
stability, is measured and is as follows: Additive Acid Modifier
Pentane Insolubles - Gms.
__________________________________________________________________________
Mannich Product none 1.5 do. oleic acid 2.5 do. isostearic acid 3.0
do. C.sub.16 -C.sub.18 mixtures of monounsaturated 3.0ds do.
C.sub.16 -C.sub.18 mixture of saturated acids 2.0
__________________________________________________________________________
Suitable alkanoic acids having 6 or more total carbon atoms are
those obtainable from the glycerides: vegetable oils and animal
fats and the wax esters by the known hydrolysis or
saponification-acidification or acid treatment processing of said
oil and fat glycerides and the wax esters (i.e. natural waxes), the
oxidation of the mono-alcohol obtainable from the simple ester of
the wax esters and known acid synthesis. Such suitable alkonic
acids, i.e. having R groups of 6 to 30 carbon atoms, include
caproic acid, caprylic acid, capric acid, hendecylic acid, lauric
acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic
acid, margaric acid, stearic acid, nonadecylic acid, arachidic
acid, medullic acid, behenic acid, lignoceric acid, pentacosoic
acid, cerotic acid, heptacosoic acid, monocosoic acid, montanic
acid, and melissic acid. Many of said alkanoic acids are obtained
first in mixtures of two, three or more alkanoic acids of different
carbon contents from said glycerides and wax esters. Said mixtures
can be used in this invention in place of a single alkanoic acid
reactant. When said mixtures of alkanoic acids also contain
unsaturated acids it is preferred that such mixture of acids be
reduced to a product which is substantially free of
unsaturation.
Suitable alkenoic acids having a total of at least six carbon atoms
include those from hexenoic, heptenoic, octenoic, etc. acids up to
oleic (C.sub.18) and erucic (C.sub.22) acids. Also suitable are the
dimer acid of linoleic and its saturated dimer analog; dimer and
trimer acids of linolenic acid and the saturated dimer and trimer
analogs. Other polymeric acids, e.g. co-dimers of oleic and
linoleic or linolenic acids and the saturated analogs of those
dimer acids are also suitable.
The foregoing, while not an exhaustive listing of all suitable
aliphatic acid reactants of the class before defined, will provide
adequate guidance for the chemist skilled in this art and also
bring to mind other suitable aliphatic acids within the scope
before defined.
At this point an explanation of various products possible within
our invention is in order. In general, the reaction under Mannich
condensation conditions, like other chemical reactions, does not go
to theoretical completion and some portion of the reactants,
generally the amine, remains unreacted or only partially reacted as
a coproduct. Thus even when a portion of a mono-functional amine
reactant (one having only one ##SPC11##
group) is used either the portion of unreacted amine or its partial
reaction product (co-product) there appears to be a sufficiently
reactive amine species to react with the aliphatic acid to form a
stable oil soluble product that appears to enhance the total
product in the manner before mentioned. Such enhancement is
achieved with relatively small amounts of the aliphatic acid
relatively small, for example in the range of 0.01 to 0.03 mole
aliphatic acid per mole of high molecular weight alkyl-substituted
hydroxy aromatic compound before described as reactant (1).
Under conditions at which water splits out, the aliphatic acid
reacts with such H.sub.2 N- and/or ##SPC12##
groups to form an amide linkage. An imidazo: ##SPC13##
linkage is possible. For example when the aliphatic acid reacts
with two H.sub.2 N- groups, or one each of H.sub.2 N- and
##SPC14##
groups are separated by two or three carbon atoms as in moiety
derived from ethylene diamine, ethylene polyamines, propylene 1,2-
and 1,3-diamines, propylene polyamines, 1,2- or 1,3 -diaminobenzene
or reacts with two molecules each having one ##SPC15##
or H.sub.2 N- group. For example, the moiety derived from an
ethylene diamine (in this case from both ethylene diamine and
ethylene polyamine): ##SPC16##
or from a propylene diamine (likewise in this case from both
propylene diamine and propylene polyamine): ##SPC17##
The foregoing formation of the imidazo linkage can be illustrated
by the reactions of an alkanoic acid ##SPC18##
(e.g. stearic wherein R has 17 carbon atoms) and
N-(2-hydroxy-5-polybutylbenzyl) ethylene and propylene diamines
wherein Z is said 2-hydroxy-5-polybutylbenzyl group in the
following equation: ##SPC19##
The cyclic product of Equation I is
1-(2-hydroxy-5-polybutylbenzyl)-2-n-heptadecylimidazoline and of
Equation 2 is
1-(2-hydroxy-5-polybutylbenzyl)-2-n-heptadecyl-1,4,5,6-tetrahydropyrimidin
e. Such specific compounds can be present in the reaction mixture
resulting from the reaction of (1) polybutylphenol, (2) ethylene
diamine or 1,3-propylene diamine, (3) formaldehyde and (4) stearic
acid in the respective reactant mole ratio of 1.0:1.0:1.0:1.0 but
other related products can also be and are, in general, also
present in admixture thereof. Mixtures of related products do
generally form when the four classes of reactants (1), (2), (3) and
(4) before defined are used broadly in the respective molar ratio
of reactants 1.0:1.0-10:1.0-10:0.01-10.0. Hence the products of
this invention cannot be properly characterized with preciseness by
chemical structural formula but rather must be characterized as
reaction products.
The following examples are illustrative of preferred embodiments of
the present invention.
EXAMPLE I
There were combined, with stirring, at a temperature of 180.degree.
F., 2300 grams (0.66 mole) of a 1,600 molecular weight polybutyl
substituted phenol (46% polybutyl phenol, 54% polybutene and 690
grams of a solvent-extracted 5W mineral oil) 115 grams (0.61 mole)
tetraethylene pentamine, and 93 grams (0.33 mole; equivalent 0.5
mole per mole polybutyl phenol) oleic acid. Thereafter, 90 ccs.
(1.2 mole) formaldehyde were slowly added, and the temperature
raised to 300.degree. F., with nitrogen bubbled through the mixture
at the rate of 2 cubic feet per hour (CFH). After heating at
300.degree. F. for 3 hours, a filter-aid, such as Celite, was added
and the mixture filtered. The recovered filtrate had a nitrogen
content of 1.24%, a SSU viscosity at 210.degree. F. of 677, and was
crystal clear.
EXAMPLE II
The method of Example I was repeated, except that 1,540 grams
(0.444 mole) of the polybutyl phenol, 460 grams of the mineral oil,
77 (0.41 mole) grams of tetraethylene pentamine, 62 (0.220 mole;
equivalent 0.5 mole per mole polybutyl phenol) grams oleic acid,
and 60 ccs. (0.816 mole) formaldehyde were used. The recovered
filtrate was crystal clear, contains 1.2% nitrogen and had a SSU
viscosity at 210.degree. F. of 679.
EXAMPLE III
400 grams (0.111 mole) of a 1,600 molecular weight polybutyl
substituted phenol (44.5% polybutyl phenol, 55.5% polybutene and 86
grams of a solvent-extracted 5W mineral oil) 8 grams (0.028 mole;
equivalent 0.25 mole per mole polybutyl phenol) oleic acid, and
19.3 grams (0.102 mole) tetraethylene pentamine were admixed at
180.degree.F. 15 ccs. (0.204 mole) formaldehyde were then added,
the temperature raised to 320.degree. F., and maintained at said
temperature for 3 hours, while introducing nitrogen at the rate of
0.5 CFH. A filter-aid was added and the product filtered. The
recovered filtrate was crystal clear, contained 1.15% nitrogen, and
had a SSU viscosity at 210.degree. F. of 827.
EXAMPLE IV
A mixture of 400 grams of a polybutyl phenol, as used in Example
III, 96 grams of a solvent-extracted 5W mineral oil, and 19.3 grams
(0.102 mole) tetraethylene pentamine was heated to 150.degree. F.,
and 15 ccs. (0.204 mole) formaldehyde added. The mixture was then
heated to 220.degree. F. and 16 grams (0.056 mole; equivalent 0.50
mole per mole polybutyl phenol) added, and the resultant mixture
heated at 300.degree.-320.degree. F. for 3 hours while bubbling
nitrogen through the reaction mixture at the rate of 0.5 CFH. At
the end of 3 hours, a filter-aid was added and the mixture
filtered. The recovered filtrate was crystal clear, contained 1.24%
nitrogen, and had a SSU viscosity at 220.degree. F. of 739.
EXAMPLE V
2,395 grams (0.666 mole) of a polybutyl phenol, as used in Example
III, 328 grams of a solvent-extracted 5W mineral oil, 24 grams
(0.084 mole; equivalent to 0.125 mole per mole of the polybutyl
phenol) oleic acid, and 116 grams (0.612 mole) tetraethylene
pentamine were mixed at a temperature of 180.degree. F., and then
90 ccs. (1.21 mole) formaldehyde were added. The reaction mixture
was then heated to 340.degree.-360.degree. F., and maintained at
such temperature for 4 hours, while nitrogen at the rate of 0.5 CFH
was bubbled through the reaction mixture. A filter-aid was added,
and the mixture filtered. The recovered filtrate was crystal clear,
contained 1.4% nitrogen, and had a SSU viscosity at 210.degree. F.
of 1070.
EXAMPLE VI
476 grams (0.132 mole) of a polybutyl phenol, as used in Example
III, 84 grams of a solvent-extracted 5W mineral oil, 19 grams
(0.066 mole; equivalent to 0.5 mole per mole of the polybutyl
phenol) stearic acid, and 23 grams (0.122 mole) tetraethylene
pentamine were admixed at 180.degree. F., and then 18 ccs. (0.24
mole) formaldehyde added. The reaction mixture was then heated to
300.degree. F. and reacted at said temperature for 3 hours, while
nitrogen at the rate of 0.5 CFH. Filter-aid was then added and the
mixture filtered. The recovered filtrate was clear, contained 1.22%
nitrogen and had a SSU viscosity at 210.degree. F. of 957.
EXAMPLE VII
238 grams (0.066 mole) of a polybutyl phenol, as used in Example
III, 37 grams of a solvent extracted 5W mineral oil, 5.7 grams
(0.033 mole; equivalent to 0.5 mole per mole of the polybutyl
phenol) capric acid, and 11.5 grams (0.061 mole) tetraethylene
pentamine were mixed at 180.degree. F., and then 9.0 ccs. (0.12
mole) formaldehyde added. The reaction temperature was raised to
300.degree. F. and maintained at said temperature for 3 hours while
blowing with nitrogen at the rate of 0.5 CFH. Filter-aid was added,
and the reaction mass filtered. The recovered filtrate was crystal
clear, contained 1.48% nitrogen, and had a SSU viscosity at
210.degree. F. of 978.
EXAMPLE VIII
Same procedure as used in Example VII, but using 7.5 grams (0.033
mole; equivalent to 0.5 mole per mole of the polybutyl phenol)
myristic acid (in place of capric acid) and 40 grams of the mineral
oil. The recovered filtrate was crystal clear, contained 1.4%
nitrogen, and had a SSU viscosity at 210.degree. F. of 967.
EXAMPLE IX
Same procedure as used in Example VII, but using 8.5 grams (0.033
mole; equivalent to 0.5 mole per mole of the polybutyl phenol)
palmitic acid (in place of capric acid), and 41 grams of the
mineral oil. The recovered filtrate was crystal clear, had a
nitrogen content of 1.32%, and had a SSU viscosity at 210.degree.
F. of 975.
EXAMPLE X
476 grams of a polybutyl phenol, as used in Example III, 84 grams
of a solvent-extracted mineral oil, 18.6 grams (equivalent to 0.5
mole per mole of the polybutyl phenol) of a mixture of fatty acids,
consisting principally of C.sub.16 and C.sub.18 monobasic acids,
marked as "Emery 894" by Emery Industries, Inc., and 23 grams of
tetraethylene pentamine were mixed together and heated to
170.degree. F. Eighteen cubic centimeters formaldehyde were then
added and the mixture heated to 300.degree.-320.degree. F., and
blown with nitrogen at the rate of 0.5 CFH for 2 hours. A
filter-aid was added and the mixture filtered. The recovered
filtrate was crystal clear, and had an SSU viscosity at 210.degree.
F. of 967.
The resistance to haze formation exhibited by the fatty acid
modified high molecular weight Mannich condensation products of the
present invention is demonstrated by the data in Table I below. In
this storage stability test the samples are stored at 160.degree.
F. for 14 days and then observed for their clarity.
Table I
__________________________________________________________________________
Sample Acid Moles* Clarity**
__________________________________________________________________________
Initial 14 Days @ 160.degree.F.
__________________________________________________________________________
Example I Oleic 0.5 7 7 Example VI Stearic 0.5 7 7 Example VII
Capric 0.5 7 7 Example VIII Myristic 0.5 7 7 Example IX Palmitic
0.5 7 7 Example X "Emery 894" 0.5 7 7 Control*** -- 7 5
__________________________________________________________________________
* Moles of acid per mole of the polybutyl phenol ** 7 indicates
crystal clear; 5 indicates barely transparent *** High molecular
weight Mannich condensation product prepared without fatty acid
modifier.
A lubricating oil composition containing a fatty acid modified high
molecular weight Mannich condensation product of the present
invention was submitted to the Caterpiller 1-H Test. This test, a
480 hour test, conducted with a high-speed, super-charged
Caterpillar diesel engine, is designed to measure the high
temperature detergency properties of a crankcase lubricating oil
for qualification under Army Ordinance Specification M1.L-2104B.
The performance of a candidate lubricating oil formulation is
determined by inspection of piston top ring grooves for carbon
deposit which is measured and percent filling determined. The
extent of varnish lacquer deposit on piston lands and in the lower
grooves is evaluated. To qualify, a lubricating oil formulation
test should result in no more than, and desirably, less than 30%
carbon deposit in the top ring groove. Varnish is the second groove
and on the first land should not exceed 50%. Below this the piston
must be clean.
The following oil formulation was used in the Caterpillar 1-H
Test:
Solvent-extracted SAE5 Oil 23.03% (Vol.) Solvent-extracted SAE10
Oil 70.00% do. Fatty acid modified product of Example I 4.00% do.
Magnesium Sulfonate 1.00% do. Zinc dialkyl dithiophosphate 0.88%
do. Pour-point Depressor* 0.50% do. Silicone Polymer Anti-foam
Agent 5 ppm *Wax alkylated naphthalene
The results of the "Caterpillar 1-H Test" using the above
formulation is shown in the following Table II.
For comparison, values obtained with a lubricating oil composition
containing an unmodified high molecular weight Mannich condensation
product are indicated in parentheses. The formulation of this oil
composition was as follows:
Mineral lubricating oil base 94.5% (Vol.) Unmodified high molecular
weight 3.5% do. Mannich condensation product Zinc dialkyl
dithiophosphate 0.7% do. Barium Sulfonate 1.3% do.
TABLE II
__________________________________________________________________________
Grooves 240 Hours
__________________________________________________________________________
1 Top groove fill-2% (5%) Top groove fill-8% (44%) 2 Clean (27%)
Clean (22%) 3 Clean (Clean) Clean (Clean) 4 Clean (Clean) Clean
(Clean) Lands
__________________________________________________________________________
1 Clean (12% AL*, LAL 14%) Clean (2% BIL, 21% AL, 17% LAL, 60%
Clean) 2 Clean Clean 3 Clean Clean Undercrown Deposits
__________________________________________________________________________
50% Light-Very light 25% Light Amber Lacquer Amber Lacquer 25%
Medium Amber Lacquer Pass (Fail)
__________________________________________________________________________
* AL-Amber Lacquer LAL-Light Amber Lacquer BIL-Black Lacquer
Another lubricating oil composition containing the fatty acid
modified high molecular weight Mannich condensation product
described in Example II, supra, was tested in the so-called "289
Ford Test." This test, made in a Ford 289 cubic inch displacement
engine, is conducted in the same manner as the so-called "Lincoln
MS V Test Sequence," described in U.S. Pat. No. 3,442,808, except
for the apparent difference in the test engines. The "289 Ford
Test" is more severe with respect to both sludge and varnish
formation and deposition since the test is conducted with vapors
from the crankcase being introduced into the engine fuel intake
system by means of a positive crankcase ventilation system.
The following oil formulation was used in the "289 Ford Test":
Solvent-extracted 5W Oil 37.15% (Vol.) Solvent-extracted 10W Oil
47.00% do. Polybutene V.I. Improver 2.80% do. Acryloid V.I.
Improver & Pour-point Agent 4.95% do. Fatty acid modified
product 5.00% (Vol.) of Example II Zinc dialkyl dithiophosphate
1.10% do. Magnesium Sulfonate 2.00% do.
The result of the "289 Ford Test" using the above formulation is
shown in the following Table III. For comparison, the values
obtained with a lubricating oil composition containing an
unmodified high molecular weight Mannich condensation product are
indicated in parentheses. The formulation of this oil composition
was as follows:
Solvent-extracted 20 Oil 93.22% (Vol.) Unmodified high molecular
weight Mannich condensation product 5.00% do. Zinc dialkyl
dithiophosphate 0.78% do. Magnesium Sulfonate 1.00% do.
Table III
__________________________________________________________________________
Varnish Sludge
__________________________________________________________________________
Piston Varnish 8.5 (8.2) Rocker Arm Cover 9.8 (7.5) Rocker Arm
Cover 9.0 (9.0) Intake Manifold 9.8 (8.0) Lifter Body 6.0 Oil
Screen 10.0 (10) Cylinder Walls 8.9 (6.8) Oil Pan 9.8 (7.3) Oil Pan
9.8 (9.4) Valve Deck 9.8 (7.7) Push Rod Chamber 9.8 (7.8) Timing
Gear Cover 9.8 (7.7) Total Varnish 42.2 (39.2) Total Sludge 49.1
(39.5) Oil Pump Relief Valve 9.8 (9.3) Plugging of Oil Rings None
(none) Piston Ring Sticking None (none) Oil Consumption (Qts.) 5.35
(5.22) Lifter Deposits, Plunger Intake Valve Tip Wear:
__________________________________________________________________________
Varnish Clean (Clean) Max. 0.0027 (0.0013) Rust 9.8 (9.8) Avg.
0.0012 (0.0010) Lifter Sticking None (None) Min. 0.0005 Plugging of
Oil Screen None (None) Push Rod Plugging None (None) Blowby, CFH:
Max. 158 Avg. 152 Min. 146 Intake Valve Tulip Deposits 7.5
__________________________________________________________________________
In the above test the engine components are examined visually and
rated on a scale of 1 to 10, a value of 10 being a perfect rating
indicating no sludge or varnish. A rating of 50 for total sludge
and for total varnish is considered perfect; a rating of 60 or
lower is considered passing for screen plugging; and a rating of 50
or lower is considered passing for ring plugging. From the data in
Table III it is evident that the fatty acid modified high molecular
weight Mannich condensation products of the present invention are
more effective than the unmodified products, and are free of the
haze drawbacks.
As noted hereinbefore the products of the present invention are
useful addition agents for lubricating oils. Such lubricating oils
can be any normally liquid oleaginous lubricant, such as
hydrocarbon oils, both natural, i.e., petroleum oils, and synthetic
oils, for example, those obtained by the polymerization of olefins,
as well as synthetic lubricating oils of the alkylene oxide type,
and the polycarboxylic acid ester type, such as the oil-soluble
esters of adipic acid, sebacic acid, azelaic acid, etc.
Percentages given herein and in the appended claims are weight
percentages unless otherwise stated.
Although the present invention has been described with reference to
specific preferred embodiments thereof, the invention is not
limited thereto, but includes within its scope such modifications
and variations as come within the scope and spirit of the appended
claims.
* * * * *