AMINO PHENOL-DETERGENT/DISPERSANT COMBINATIONS AND FUELS AND LUBES CONTAINING SAME

COMBINAISONS DE DETERGENT/DISPERSANT ET D'AMINO- PHENOLS; COMBUSTIBLES ET LUBRIFIANTS QUI LES CONTIENNENT

English Abstract

ABSTRACT OF THE DISCLOSURE:
Disclosed are combinations of amino phenols,
wherein said phenols contain a substantially saturated hy-
drocarbon substituent of at least 10 aliphatic carbon atoms,
and one or more detergent/dispersants selected from the
group consisting of (I) neutral or basic metal salts of an
organic sulfur acid, phenol or carboxylic acid; (II) hydro-
carbyl-substituted amines wherein the hydrocarbyl substi-
tuent is substantially aliphatic and contains at least 12
carbon atoms; (III) acylated nitrogen-containing compounds
having a substituent of at least 10 aliphatic carbon atoms;
and (IV) nitrogen-containing condensates of a phenol, alde-
hyde and amino compound. Fuels and lubricants containing
such combinations as additives are particularly useful in
two-cycle (two-stroke) engines.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A nitrogen-containing organic composition com-
prising a combination of:
(A) at least one amino phenol of the general
formula
<IMG>
wherein R is a substantially saturated, hydro-
carbon-based substituent of at least 10 aliphatic
carbon atoms; a, b and c are each independently an
integer of one up to three times the number of
aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the
unsaturated valences of Ar; and Ar is an aromatic
moiety having 0-3 optional substituents selected
from the group consisting of lower alkyl, lower
alkoxyl,nitro, halo or combinations of two or more
of said substituents; and
(B) at least one detergent/dispersant selected
from the group consisting of
(I) at least one neutral or basic metal salt
of an organic sulfur acid, phenol or car-
boxylic acid;
(II) at least one hydrocarbyl-substituted
amine wherein the hydrocarbyl substituent is
substantially aliphatic and contains at least
12 carbon atoms with the proviso that said
amine is not the amino phenol (A);
52

(III) at least one acylated, nitrogen-
containing compound having a substituent of
at least 10 aliphatic carbon atoms made by
reacting a carboxylic acylating agent with at
least one amino compound containing at least
one <IMG> group, said acylating agent being
linked to said amino compound through an
imido, amido, amidine, or acyloxy ammonium
linkage; and
(IV) at least one nitrogen-containing
condensate of a phenol, aldehyde and amino
compound having at least one <IMG> group.
2. A composition as claimed in claim 1 wherein R
contains up to about 750 carbon atoms and there are no
optional substituents attached to Ar.
3. A composition as claimed in claim 2 wherein R is
an alkyl or alkenyl group.
4. A composition as claimed in claim 1 wherein R
contains about 30 to about 750 aliphatic carbon atoms and is
made from a homo- or interpolymer of C2-C10 olefins.
5. A composition as claimed in claim 4 wherein said
olefins are selected from the group consisting of ethylene,
propylene, butylene and mixtures thereof.
6. A composition as claimed in claim 1 wherein a, b
and c are each 1, there are zero optional substituents
attached to Ar, and Ar is a benzene nucleus.
7. A composition as claimed in claim 6 wherein R is
an alkyl or alkenyl group of at least about 30 carbon atoms
and up to about 750 carbon atoms and is derived from a homo-
or interpolymer of C2-C10 1-monoolefins.
53

8. A composition as claimed in claim 1 wherein the
amino phenol is of the formula
<IMG>
wherein R' is a substantially saturated hydrocarbon-based
substituent having an average of from about 30 to about 400
aliphatic carbon atoms, R" is a member selected from the
group consisting of lower alkyl, lower alkoxy, nitro, and
halo; and z is 0 or 1.
9. A composition as claimed in claim 8 wherein R' is a
purely hydrocarbyl aliphatic group of at least about 50
carbon atoms and is made from a polymer or interpolymer of
an olefin selected from the group consisting of C2-10 1-
monoolefins and mixtures thereof.
10. A composition as claimed in claim 9 wherein z is
0.
11. A composition as claimed in claim 1 wherein the
detergent/dispersant is (I) at least one neutral or basic
metal salt of an organic sulfur acid, phenol or carboxylic
acid.
12. A composition as claimed in claim 11 wherein the
detergent/dispersant is at least one basic metal salt of an
organic sulfonic acid or phenol.
13. A composition as claimed in claim 12 wherein the
metal is at least one alkali or alkaline earth metal.
14. A composition as claimed in claim 12 wherein the
detergent/dispersant is at least one alkaline earth metal
sulfonate.
54

15. A composition as claimed in claim 14 wherein the
sulfonate is an alkyl-substituted benzene sulfonate wherein
the alkyl group has at least about 8 carbon atoms.
16. A composition as claimed in claim 15 wherein the
amino phenol is of the formula
<IMG>
wherein R' is a substantially saturated hydrocarbon-based
substituent having an average of from about 30 to about 400
aliphatic carbon atoms, R" is a member selected from the
group consisting of lower alkyl, lower alkoxyl, nitro and
halo; and z is 0 or 1.
17. A composition as claimed in claim 1 wherein the
detergent/dispersant is at least one hydrocarbyl-substituted
amine.
18. A composition as claimed in claim 17 wherein the
hydrocarbyl amine is of the general formula
<IMG>
wherein A is hydrogen, a hydrocarbyl group of from 1 to 10
carbon atoms, or hydroxyhydrocarbyl group of from 1 to 10
carbon atoms; X is hydrogen, a hydrocarbyl group of from 1
to 10 carbon atoms, or hydroxyhydrocarbyl group of from 1 to
10 carbon atoms, and may be taken together with A to form a
ring of from 5 to 6 annular members and up to 12 carbon
atoms; U is an alkylene group of from 2 to 10 carbon atoms,
R2 is an aliphatic hydrocarbon group of from about 30 to 400
carbon atoms; a is an integer of from 0 to 10; b is an

integer of from 0 to 1; a+2b is an integer of from 1 to 10,
c is an integer of from 1 to 5 and is as an average in the
range of 1 to 4, and equal to or less than the number of
nitrogen atoms in the molecule; x is an integer of from 0 to
l; y is an integer of from 0 to 1; and x+y is equal to 1.
19. A composition as claimed in claim 18 wherein the
hydrocarbyl amine is a polyamine of the general formula
<IMG> .
20. A composition as claimed in claim 18 wherein the
amine is a monoamine of the general formula
AXNR2.
21. A composition as claimed in claim 17 wherein the
hydrocarbyl-substituted amine is a hydrocarbyl-substituted
aminohydrocarbyl morpholine of the general formula
<IMG>
wherein R2, is an aliphatic hydrocarbon group of from about
30 to about 400 carbons, A is hydrogen hydrocarbyl of from 1
to 10 carbon atoms or hydroxy hydrocarbyl group of from 1 to
10 carbon atoms and U is an alkylene group of from 2 to 10
carbon atoms.
22. A composition as claimed in claim 18 wherein the
amino phenol is of the general formula
<IMG>
wherein R' is a substantially saturated hydrocarbon-based
substituent having an average of from about 30 to about 400
56

alipnatic carbon atoms; R" is a member selected from the
group consisting of lower alkyl, lower alkoxyl, nitro and
halo; and z is 0 or 1.
23. A composition as claimed in claim 1 wherein the
detergent/dispersant is (III) at least one acylated, nitro-
gen-containing compound having a substituent of at least 10
aliphatic carbon atoms and made by reacting a carboxylic
acylating agent with at least one amino compound containing
at least one <IMG> group, said acylating agent being linked to
said amino compound through an imido, amido, amidine or
acyloxy ammonium linkage.
24. A composition as claimed in claim 23 wherein the
amino compound is an alkylene polyamine of the general
formula
<IMG>
wherein U is an alkylene group of 2 to 10 carbon atoms; each
R''' is independently a hydrogen atom, a lower alkyl group
or a lower hydroxy alkyl group, with the proviso that at
least one R''' is a hydrogen atom, and n is 1 to 10.
25. A composition as claimed in claim 24 wherein the
acylating agent is a mono- or polycarboxylic acid, or
reactant equivalent thereof, containing an aliphatic hydro-
carbyl substituent of at least about 30 carbon atoms.
26. A composition as claimed in claim 25 wherein the
substituent is made from a homo- or interpolymer of a C2-10
1-monoolefin or mixtures thereof.
27. A composition as claimed in claim 26 wherein the
homo- or interpolymer is of ethylene, propylene, 1-butene,
2-butene, isobutene or mixtures thereof.
57

28. A composition as claimed in claim 27 wherein the
amino phenol is of the formula
<IMG>
wherein R' is a substantially saturated hydrocarbon-based
substituent having an average of from about 30 to about 400
aliphatic carbon atoms located ortho or para to the hydroxyl
group; R" is a member selected from the group consisting of
lower alkyl, lower alkoxyl, nitro and halo; and z is 0 or 1.
29. A composition as claimed in claim 24 wherein the
acylating agent is at least one mono-carboxylic acid, or
reactant equivalent thereof, having from 12 to 30 carbon
atoms.
30. A composition as claimed in claim 29 wherein the
acylating agent is a mixture of fatty monocarboxylic acids,
or reactant equivalent thereof, having straight and branched
carbon chains.
31. A composition as claimed in claim 30 wherein the
amino compound is an ethylene, propylene or trimethylene
polyamine of at least 2 to about 8 amino groups or mixtures
of such polyamines.
32. A composition as claimed in claim 31 wherein the
amino phenol is of the formula
<IMG>
58

wherein R' is a substantially saturated hydrocarbon-based
substituent having an average of from about 30 to about 400
aliphatic carbon atoms; R" is a member selected from the
group consisting of lower alkyl, lower alkoxyl, nitro and
halo; and z is 0 or 1.
33. A composition as claimed in claim 1 wherein the
detergent/dispersant is a (IV) nitrogen-containing con-
densate of a phenol, aldehyde and amino compound having at
least one <IMG> group.
34. A composition as claimed in claim 33 wherein the
phenol is an alkyl-substituted phenol, the alkyl group
having at least about 30 carbon atoms.
35. A composition as claimed in claim 34 wherein the
aldehyde is formaldehyde, or a reactant equivalent thereof.
36. A composition as claimed in claim 35 wherein the
amino compound is of the formula
<IMG>
wherein U is an alkylene group of 2 to 10 carbon atoms; each
R''' is independently a hydrogen atom, a lower alkyl group
or a lower hydroxy alkyl group, with the proviso that at
least one R''' is a hydrogen atom, and n is 1 to 10.
37. A composition as claimed in claim 36 wherein the
condensate is made by first reacting the phenol with the
aldehyde in the presence of an alkaline catalyst at a temp-
erature of up to 150°, then neutralizing the intermediate
reaction mixture thus formed and finally reacting the
neutralized intermediate reaction mixture with at least one
amino compound having at least one <IMG> group.
59

38. A composition as claimed in claim 33 wherein the
amino phenol is of the formula
<IMG>
wherein R' is a substantially saturated hydrocarbon-based
substituent having an average of from about 30 to about 400
aliphatic carbon atoms; R" is a member selected from the
group consisting of lower alkyl, lower alkoxyl, nitro and
halo; and z is 0 or 1.
39. A composition as claimed in claim 37 wherein the
amino phenol is of the formula
<IMG>
wherein R' is a substantially saturated hydrocarbon-based
substituent having an average of from about 30 to about 400
aliphatic carbon atoms; R" is a member selected from the
group consisting of lower alkyl, lower alkoxyl, nitro and
halo; and z is 0 or 1.
40. A composition as claimed in claim 1 wherein the
ratio by weight of amino phenol to the total amount of
detergent/dispersant is in the range of about 1:10 to about
10:1.
41. A composition as claimed in claim 9 wherein the
ratio by weight of amino phenol to the total amount of
detergent/dispersant is in the range of about 1:10 to about
10:1.

42. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 1.
43. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 8.
44. A composition as claimed in claim 43 wherein R' is
a purely hydrocarbyl aliphatic group of at least about 50
carbon atoms and is made from a polymer or interpolymer of
an olefin selected from the group consisting of C2-10
1-monoolefin and mixtures thereof.
45. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 11.
46. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 15.
47. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 16.
48. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 18.
61

49. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 21.
50. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 22.
51. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 23.
52. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 25.
53. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 30.
54. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 32.
55. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 33.
62

56. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 37.
57. A lubricant composition for two-cycle engines
comprising a major amount by weight of at least one oil of
lubricating viscosity and a minor amount by weight of a
composition as claimed in claim 38.
58. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 42.
59. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 43.
60. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 44.
61. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 45.
62. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 48.
63. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 49.
64. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 51.
63

65. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 52.
66. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 53.
67. A lubricant-fuel mixture for use in two-cycle
internal combustion engines wherein the lubricant is the
composition claimed in claim 56.
68. In the method for lubricating a two-cycle internal
combustion engine, the improvement which comprises using a
lubricant composition as claimed in claim 42.
69. In the method for lubricating a two-cycle internal
combustion engine, the improvement which comprises using a
lubricant composition as claimed in claim 43.
70. In the method for lubricating a two-cycle internal
combustion engine, the improvement which comprises using a
lubricant composition as claimed in claim 44.
71. In the method for lubricating a two-cycle internal
combustion engine, the improvement which comprises using a
lubricant composition as claimed in claim 52.
72. In the method for lubricating a two-cycle internal
combustion engine, the improvement which comprises using a
lubricant composition as claimed in claim 53.
73. In the method for lubricating a two-cycle internal
combustion engine, the improvement which comprises using a
lubricant composition as claimed in claim 56.
64

74. A composition as claimed in claim 1 wherein the
amino phenol (A) is made by:
(I) nitrating with at least one nitrating agent
at least one compound of the formula
<IMG> ,
wherein R is a substantially saturated hydrocarbon-based
group of at least 10 aliphatic carbon atoms; a and c are
each independently an integer of 1 up to three times the
number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar'; and Ar' is an aromatic moiety having 0 to 3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, nitro, and halo, or combinations
of two or more optional substituents, with the provisos that
(a) Ar' has at least one hydrogen atom directly bonded to a
carbon atom which is part of an aromatic nucleus, and (b)
when Ar is a benzene having only one hydroxyl and one R
substituent, the R substituent is ortho or para to said
hydroxyl substituent, to form a first reaction mixture
containing a nitro intermediate, and
(II) reducing at least about 50% of the nitro
groups in said first reaction mixture to amino groups.
75. A composition as claimed in claim 11 wherein the
amino phenol (A) is made by:
(I) nitrating with at least one nitrating agent
at least one compound of the formula
<IMG> ,

wherein R is a substantially saturated hydrocarbon-based
group of at least 10 aliphatic carbon atoms; a and c are
each independently an integer of 1 up to three times the
number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar'; and Ar' is an aromatic moiety having 0 to 3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, nitro, and halo, or combinations
of two or more optional substituents, with the provisos that
(a) Ar' has at least one hydrogen atom directly bonded to a
carbon atom which is part of an aromatic nucleus, and (b)
when Ar is a benzene having only one hydroxyl and one R
substituent, the R substituent is ortho or para to said
hydroxyl substituent, to form a first reaction mixture
containing a nitro intermediate, and
(II) reducing at least about 50% of the nitro
groups in said first reaction mixture to amino groups.
76. A composition as claimed in claim 17 wherein the
amino phenol (A) is made by:
(I) nitrating with at least one nitrating agent
at least one compound of the formula
<IMG> ,
wherein R is a substantially saturated hydrocarbon-based
group of at least 10 aliphatic carbon atoms; a and c are
each independently an integer of 1 up to three times the
number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar'; and Ar' is an aromatic moiety having 0 to 3
66

optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, nitro, and halo, or combinations
of two or more optional substituents, with the provisos that
(a) Ar' has at least one hydrogen atom directly bonded to a
carbon atom which is part of an aromatic nucleus, and (b)
when Ar is a benzene having only one hydroxyl and one R
substituent, the R substituent is ortho or para to said
hydroxyl substituent, to form a first reaction mixture
containing a nitro intermediate, and
(II) reducing at least about 50% of the nitro
groups in said first reaction mixture to amino groups.
77. A composition as claimed in claim 25 wherein the
amino phenol (A) is made by:
(I) nitrating with at least one nitrating agent
at least one compound of the formula
<IMG>
wherein R is a substantially saturated hydrocarbon-based
group of at least 10 aliphatic carbon atoms: a and c are
each independently an integer of 1 up to three times the
number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar'; and Ar' is an aromatic moiety having 0 to 3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, nitro, and halo, or combinations
of two or more optional substituents, with the provisos that
(a) Ar' has at least one hydrogen atom directly bonded to a
carbon atom which is part of an aromatic nucleus, and (b)
when Ar is a benzene having only one hydroxyl and one R
67

substituent, the R substituent is ortho or para to said
hydroxyl substituent, to form a first reaction mixture
containing a nitro intermediate, and
(II) reducing at least about 50% of the nitro
groups in said first reaction mixture to amino groups.
78. A composition as claimed in claim 33 wherein the
amino phenol (A) is made by:
(I) nitrating with at least one nitrating agent
at least one compound of the formula
<IMG> ,
wherein R is a substantially saturated hydrocarbon-based
group of at least 10 aliphatic carbon atoms; a and c are
each independently an integer of 1 up to three times the
number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar'; and Ar' is an aromatic moiety having 0 to 3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, nitro, and halo, or combinations
of two or more optional substituents, with the provisos that
(a) Ar' has at least one hydrogen atom directly bonded to a
carbon atom which is part of an aromatic nucleus, and (b)
when Ar is a benzene having only one hydroxyl and one R
substituent, the R substituent is ortho or para to said
hydroxyl substituent, to form a first reaction mixture
containing a nitro intermediate, and
(II) reducing at least about 50% of the nitro
groups in said first reaction mixture to amino groups.
68

79. A composition as claimed in claim 1 wherein the
amino phenol is made by reducing at least about 50% of the
nitro groups to amino groups in a compound or mixture of
compounds of the formula
<IMG>
wherein R is a substantially saturated hydrocarbon-based
substituent of at least 10 aliphatic carbon atoms; a, b and
c are each independently an integer of 1 up to three times
the number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar; and Ar is an aromatic moiety having 0 to 3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, halo, or combinations of two or
more of said optional substituents; with the proviso that
when Ar is a benzene nucleus having only one hydroxyl and
one R substituent, the R substituent is ortho or para to
said hydroxyl substituent.
80. A composition as claimed in claim 11 wherein the
amino phenol is made by reducing at least about 50% of the
nitro groups to amino groups in a compound or mixture of
compounds of the formula
<IMG>
wherein R is a substantially saturated hydrocarbon-based
substituent of at least 10 aliphatic carbon atoms; a, b and
c are each independently an integer of 1 up to three times
the number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
69

valences of Ar; and Ar is an aromatic moiety having 0 to 3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, halo, or combinations of two or
more of said optional substituents; with the proviso that
when Ar is a benzene nucleus having only one hydroxyl and
one R substituent, the R substituent is ortho or para to
said hydroxyl substituent.
81. A composition as claimed in claim 17 wherein the
amino phenol is made by reducing at least about 50% of the
nitro groups to amino groups in a compound or mixture of
compounds of the formula
<IMG>
wherein R is a substantially saturated hydrocarbon-based
substituent of at least 10 aliphatic carbon atoms; a, b and
c are each independently an integer of 1 up to three times
the number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar; and Ar is an aromatic moiety having 0 to 3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, halo, or combinations of two or
more of said optional substituents; with the proviso that
when Ar is a benzene nucleus having only one hydroxyl and
one R substituent, the R substituent is ortho or para to
said hydroxyl substituent.
82. A composition as claimed in claim 25 wherein the
amino phenol is made by reducing at least about 50% of the
nitro groups to amino groups in a compound or mixture of
compounds of the formula

<IMG>
wherein R is a substantially saturated hydrocarbon-based
substituent of at least 10 aliphatic carbon atoms; a, b and
c are each independently an integer of 1 up to three times
the number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar; and Ar is an aromatic moiety having 0 to 3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, halo, or combinations of two or
more of said optional substituents; with the proviso that
when Ar is a benzene nucleus having only one hydroxyl and
one R substituent, the R substituent is ortho or para to
said hydroxyl substituent.
83. A composition as claimed in claim 33 wherein the
amino phenol is made by reducing at least about 50% of the
nitro groups to amino groups in a compound or mixture of
compounds of the formula
<IMG>
wherein R is a substantially saturated hydrocarbon-based
substituent of at least 10 aliphatic carbon atoms; a, b and
c are each independently an integer of 1 up to three times
the number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar; and Ar is an aromatic moiety having 0 to 3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxyl, halo, or combinations of two or
more of said optional substituents; with the proviso that
when Ar is a benzene nucleus having only one hydroxyl and
one R substituent, the R substituent is ortho or
para to said hydroxyl substituent.
71

Description

BACKGROUND OF THE INVENTION
(1) Field of the Invention
This invention relates to additive combinations useful
in oils of lubricating viscosity and normally liquid fuels.
More particularly, it relates to additive combinations of
amino phenols with certain detergent/dispersants and to oils
and fuels containing same which are especially useful in
two-cycle engines.
(2) Prior Art
The book "Lubricant Additives" by M. W. Ranney, pub-
lished by Noyes Data Corporation of Parkridge, New Jersey
(1973), discloses a number of metal salts of various sul-
fonic and carboxylic acids and of phenols which are useful
as detergent/dispersants in lubricating oil products. The
book also entitled "Lubricant Additives" by C. V. Smallheer
and R. K. Smith, published by the Lezius-Hiles Co. of Cleve-
land, Ohio ~1967), similarly discloses a number of detergent/
dispersants including sulfonates, phenates and carboxylates
as well as alkyl and alkenyl succinimides and other high
; 20 molecular weight amides and polyamides which are useful as
dispersants. Other literature, particularly patents, which
also disclose similar subject matter will be noted at appro-
priate points in the following specification.
(3) General Background
It is well knowm that additives are commonly added to
engine lubricant and fuel compositions to prevent deposit
formation on engine and fuel system surfaces with which the
lubricant or fuel may come in contact. Such deposits inter-

fere with proper circulation of lubricants in the engine.
They can also act as abrasives to increase wear of engine
parts; in extreme cases, such deposits may even hinder
movement of engine parts. Deposits from fuels can interfere
with proper carburetor operation, increase spark plug fouling,
and the like.
Among the engines which utilize such lubricants and
fuels are two-cycle (two-stroke), spark-ignited internal
combustion engines including rotary engines such as the
Wankel-type engine. Use of these types of engines has
steadily increased over the past several decades and they
are presently found in power lawn mowers and other power
operated garden equipment, power chain saws, pumps, elec-
trical generators, marine out-board engines, snow-mobiles,
motorcycles, other light-weight wheeled vehicles and the
like.
The increasing use of two-cycle engines, coupled with
the increasing severity of the conditions under which they
have been operated and the need to maximize usuage of petro-
leum-derived materials in the face of increasing shortages,
has led to an increasing demand for oils and fuels which
adequately lubricate such engines (it is a common practice
to add the oils used to lubricate such engines to the fuel).
Among the problems associated with the lubrication of
~wo-cycle engines are piston ring sticking, rusting, lubri-
cation failure of connecting rod and main bearings, and
deposit formation as noted above. The formation of varnish
is a particularly vexatious problem since the build-up of

l`U~
varnish on piston and cylinder walls can cause loss of
compression through seal failing. This is particularly
damaging in two-cycle engines since they depend on suction
to draw the new fuel charge into the exhausted cylinder.
The unique problems and techniques associated with the
lubrication of two-cycle engines has led to a recognition in
the art of two-cycle engine lubricants (and fuels containing
same) as distinct types of lubricants and fuels. Similarly,
additive concentrates for treating such fuels and lubricants
have also been recognized to be a distinct field in the art.
See, for example, U.S. Patents 3,085,975; 3,004,837; and
3,753,905.
The inventions described herein include novel additive
combinations for lubricating oils and normally liquid fuels,
lS in general, and particularly for oils and fuels used in two-
cycle engines.
(4) Objects
Therefore, it is an object of this invention to provide
novel additive combinations.
It is a further object of this invention to provide
novel lubricants, fuels and additive concentrates containing
the novel additive combinations.
It is a particular object of this invention to provide
novel additive combinations and lubricants and fuels con-
taining the same for use in $wo-cycle, spark-ignited engines
as well as novel means for operating such engines.
Other objects will be apparent to those skilled in the
art upon review of the present specification.

~3~
SUMMARY OF THE INVENTION
This invention comprises a nitrogen-containing organic
composition comprising a combination of:
(A) at least one amino phenol of the general formula
(I~)c
(R)a Ar (NH2)b Formula I
wherein ~ is a substantially saturated, hydrocarbon-based
substituent of at least 10 aliphatic carbon atoms; a, b and
c are each independently an integer of one up to three times
the number of aromatic nuclei present in Ar, with the pro-
viso that the sum of a, b and c does not exceed the unsatis-
fied valences of Ar; and Ar is an aromatic moiety having 0-3
optional substituents selected from the group consisting of
lower alkyl, lower alkoxy, nitro, halo or combinations of
two or more of said substituents; and
(B) at least one detergent/dispersant selected from
the group consisting of
(I) at least one neutral or basic metal salt of an
organic sulfur acid, phenol or carboxylic acid;
(II) at least one hydrocarbyl-substituted amine wherein
the hydrocarbyl substituent is substantially aliphatic
and contains at least twelve carbon atoms, with the
proviso that said amine is not the amino phenol (A);
(III) at least one acylated, nitrogen-containing com-
pound having a substituent of at least 10 aliphatic
carbon atoms made by reacting a carboxylic acid acylat-
ing agent with at least one amino compound containing
at least one~ NH group, said acylating agent being
-- 4 --

linked to said amino compound through an imido, amido,
amidine, or acyloxy ammonium linkage; and
(IV) at least one nitrogen-containing condensate of a
phenol, aldehyde and amino compound having at least one
>NH group.
Lubricants based on oils of lubricating viscosity and
normally liquid engine fuels as well as additive concen-
trates containing the above-described combinations are also
part of this invention.
DETAILED DESCRIPTION OF THE INVENTION
(A) The Amino Phenols
The aromatic moiety, Ar, of Formula I can be a single
aromatic nucleus ~uch as a benzene nucleus, a pyridine
nucleus, a thiophene nucleus, a l,2,3,4-tetrahydronaphtha-
lene nucleus, etc., or a polynuclear aromatic moiety. Such
polynuclear moieties can be of the fused type; that is,
wherein at least one aromatic nucleus is fused at two points
to another nucleus such as found in naphthalene, anthracene,
the azanaphthalenes, etc. Alternatively, such polynuclear
aromatic moieties can be of the linked type wherein at least
two nuclei (either mono- or polynuclear) 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, keto linkages, sulfide link-
ages, polysulfide linkages of 2 to 6 sulfur atoms, sulfinyl
linkages, sulfonyl linkages, methylene linkages, alkylene
linkages, di-(lower alkyl1methylene linkages, lower alkylene

ether linkages, alkylene keto linkages, lower alkylene
sulfur linkages, lower alkylene polysulfide linkages of 2 to
6 carbon atoms, amino linkages, pol-Famino linkages and
mixtures of such divalent bridging linkages. In certain
instances, more than one bridging linkage can be present in
Ar between aromatic nuclei. For example, a fluorene nucleus
has two benzene nuclei linked by both a methylene linkage
and a covalent bond. Such a nucleus may be considered to
have 3 nuclei but only two of them are aromatic. Normally,
however, Ar will contain only carbon atoms in the aromatic
nuclei per se (plus any lower alkyl or alkoxy substituent
present).
The number of aromatic nuclei, fused, linked or both,
in Ar can play a role in determining the integer values of
a, b and c in Formula I. For example, when Ar contains a
single aromatic nucleus, a, b and c are each independently 1
to 4. When Ar contains two aromatic nuclei, a, b and c can
each be an integer of 1 to 8, that is, up to three times the
number of aromatic nuclei present (in naphthalene, 2). With
a tri-nuclear Ar moiety, a, b and c can each be an integer
of 1 to 12. For example, when Ar is a biphenyl or a naphthyl
moiety, a, b and c can each independently be an integer of 1
to 8. The values of a, b and c are obviously limited by the
fact that their sum cannot exceed the total unsatisfied
valences of Ar.

The single ring aromatic nucleus which can be the Ar
moiety can be represented by the general formula
ar(Q)m
wherein ar represents a single ring aromatic nucleus (e.g.,
benzene) of 4 to 10 carbons, each Q independently represents
a lower alkyl group, lower alkoxy group, nitro group, or
halogen atom, and m is O to 3. As used in this specifi-
cation and appended claims, "lower" refers to groups having
7 or less carbon atoms such as lower alkyl and lower alkoxyl
groups. Halogen atoms include fluorine, chlorine, bromine
and iodine atoms; usually, the halogen atoms are fluorine
and chlorine atoms.
Specific examples of single ring Ar moieties are
the following:
HI~H H~H H~CH
H ~ Me H~ Cl H ~ H
H2 1 / CH2- CH2
~L H2 ~ \CH2- IH2
~ etc.

wherein Me is methyl, Et is ethyl, Pr is n-propyl, and
Nit is nitro.
When Ar is a polynuclear fused-ring aromatic moiety, it
can be represented by the general formula
ar~ ar~m~ (Q)mm~
wherein ar, Q and m are as defined hereinabove, m' is 1 to
4 and ~ represent a pair of fusing bonds fusing two rings
so as to make two carbon atoms part of the rings of each of
two adjacent rings. Specific examples of fused ring aromatic
moieties Ar are:
H
H ~ ~ H H ~
H ~ H
MeO
~1 ~ `~-M Me 1 1 1
H ~ H H ~ ~ - H
1 1 H
~ ~ H ~ ~ H
R ~ ~ MeO
H H
etc .
When the aromatic moiety Ar is a linked polynuclear
aromatic moiety it can be represented by the general formula
ar~-Lng-ar-tw(Q)mw
wherein W iS an integer Of 1 to about 20, ar is as described
aboYe with the proviso that there are at least 3 unsatisfied
(i.e., free) valences in the total of ar groups, Q and m are
8 --

as defined hereinbefore, and each Lng is a bridging linkage
individually chosen from the group consisting of carbon-to-
carbon single bonds, ether linkages ~e.g. -o-), keto link-
o
ages (e.g., -C-), sulfide linkages (e.g., -S-), polysulfide
linkages of 2 to 6 sulfur atoms (e.g., -S2-6-), sulfinyl
linkages (e.g., -StO)-), sulfonyl linkages (e.g., -S(0)2-),
lower alkylene linkages (e.g., -CH2-, -CH2-CH2-, -CH-CH-,
etc.), di(lower alkyl)-methylene linkages (e.g., CR2-~,
lower alkylene ether linkages (e.g., -CH20-, -CH20-CH~-,
-CH 2 -CH20-, -CH2CH 2 OCH2CH2~, -CH2CHOCH2CH-, -CH2CHOCHCH 2 -
R R R R
etc.), iower alkylene sulfide linkages (e.g., wherein
one or more -O-'s in th~ lower alkylene ether linkages is
replaced with an -S- atsm), lower alkylene polysulfide
linkages (e.g., wherein one or more -O-'s is replaced with
a -S -6 group)~ amino linkages (e.g., -N-, 7 -CH2N-,
H R
-CH2lCH2-t -alk-N-, where alk is lower alkylene, etc.),
polyamino linkages (e.g., -N~alkN)I-lO, where the unsatis-
fied free N valences are taken up with H atoms or R groups),
and mixtures of such bridging linkages (each R being a
lower alkyl group). ~t is also possible that one or more of
the ar groups in the above-linked aromatic moiety can be
replaced by fused nuclei such as ar ~C ar 2 m'
Specific examples of linked moieties are:
_ g _

H I ~ ~ H
H H H H
_ CH 2~
H2
H ~ I~; 1 H
M~;~Me~ I - I o
s 4 c ~
H H
H~ o ~ etc.
Usually all these Ar moieties are unsubstituted except
for the R, -OH and -NH2 groups (and any bridging groups).
For such reasons as cost, availability, perfor~ance,
etc., the Ar moiety is normally a benzene nucleus, lower
--10 --

alkylene bridged benzene nucleus, or a naphthalene nucleus.
Thus, a typical Ar moiety is a benzene or naphthalene
nucleus having 3 to 5 unsatisfied valences, so that one or
two of said valences may be satisfied by a hydroxyl group
with the remaining unsatisfied valences being, insofar as
possible, either ortho or para to a hydroxyl group. Pre-
ferably, Ar is a benzene nucleus having at least 3 unsatisfied
valences so that one can be satisfied by a hydroxyl group
with the remaining 2 or 3 being either ortho or para to the
hydroxyl group.
The Substantially Saturated Hydrocarbon-based Group R
The amino phenols of the present invention contain,
directly bonded to the aromatic moiety Ar, a substantially
saturated monovalent hydrocarbon-based group R of at least
about 10 aliphatic carbon atoms. This R group can have up
to about 400 aliphatic carbon atoms. More than one such
group can be present, but usually, no more than 2 or 3 such
groups are present for each aromatic nucleus in the aromatic
moiety Ar. The total number of R groups present is indi-
cated by the value for "a" in Formula I. Usually, the
hydrocarbon-based group has at least about 30, more typi-
cally, at least about 50 aliphatic carbon atoms and up to
about 750, more typically, up to about 300 aliphatic carbon
atoms.
&enerally, the hydrocarbon-based groups R are made
from homo- or interpolymers (e.g., copolymers, terpoly-
mers) of mono- and di-olefins having 2 to 10 carbon
atoms, such as ethylene, propylene, butene-l, isobutene,
butadiene, isoprene, l-hexene, l-octene, etc. Typically,
these olefins are l-monoolefins such as homopolymers
of ethylene. The R groups can also be derived from
-- 11 --

lU~
the halogenated (e.g., chlorinated or brominated) analogs of
such homo- or interpolymers. The R groups can, however, be
made from other sources, such as monomeric high molecular
weight alkenes (e.g., l-tetracontene) and chlorinated
analogs and hydrochlorinated analogs thereof, aliphatic
petroleum fractions, particularly paraffin waxes and cracked
and chlorinated analogs and hydrochlorinated analo~s thereof,
white oils, synth~tic alkenes such as those produced by the
Ziegler-Natta process (e.g., poly(ethylene) greases) and
other sources known to those skilled in the art. Any un-
saturation in the R groups may be reduced or eliminated by
hydrogenation according to procedures known in the art
before the nitration step described hereafter.
As used herein, the term "hydrocarbon_based" denotes a
group having a carbon atom directly attached to the re-
mainder of the molecule and having a predominantly hydro-
carbon character within the context of this invention.
Therefore, hydrocarbon-based groups can contain up to one
non-hydrocarbon radical for every ten carbon atoms provided
this non-hydrocarbon radical does not significantly alter
the predominantly hydrocarbon character of the group. Those
skilled in the art will be aware of such radicals, which
include , for example, hydroxyl, halo (especially chloro and
fluoro), alkoxyl, alkyl mercapto, alkyl sulfoxy, etc.
Usually, however, the hydrocarbon-based groups R are purely
hydrocarbyl and contain no such non-hydrocarbyl radicals.
The hydrocarbon-based group~ R are substantially
saturated. By substantially saturated it is meant that
the group contains no more than one carbon-to-carbon
unsaturated bond for every ten carbon-to-carbon single
bonds present. Usually, they contain no more than
. ,~

One carbon-to-carbon non-aromatic unsaturated bond for every
50 carbon-to-carbon bsnds present.
The hydrocarbon-based groups of the amino phenols of
this invention are also substantially aliphatic in nature,
that is, they contain no more than one non-aliphatic moiety
(cycloalkyl, cycloalkenyl or aromatic) group of six or less
carbon atoms for every ten carbon atoms in the ~ group.
Usually, however, the R groups contain no more than one such
non-aliphatic group for every fifty carbon atoms, and in
many cases, they contain no such non-aliphatic groups at
all; that is, the typical R groups are purely aliphatic~
Typically, these purely aliphatic R groups are alkyl or
alkenyl groups.
Specific examples of the substantially saturated
hydrocarbon-based R groups are the following:
a tetra(propylene) group
a tri~isobutene) group
a tetracontanyl group
a henpentacontanyl group
a mixture of poly(ethylene/propylene) groups of
about 35 to about 70 carbon atoms
a mixture of the oxidatively or mechanically
degraded poly(ethylene/propylene) groups of about
35 to about 70 carbon atoms
a mixture of poly(propylene/l-hexene) groups of
about 80 to about 150 carbon atoms
a mixture of poly(isobutene) ~roups having between
20 and 32 carbon atoms
a mixture of poly(isobutene) groups having an
average of 50 to 75 carbon atoms

A preferred source of the group R are poly(isobutene)s
obtained by polymerization of a C4 refinery stream having a
butene content of 35 to 75 weight percent and isobutene
content of 15 to 60 weight percent in the presence of a
Lewis acid catalyst such as aluminum trichloride or boron
trifluoride. These polybutenes contain predominantly
(greater than 80% of total repeating units) isobutene
repeatin~ units of the configuration
CH3
CH 2 - C -
CH3
The attachment of the hydrocarbon-based group R to the
aromatic moiety Ar of the amino phenols of this invention
can be accomplished by a number of techniques well known to
tho~e skilled in the art. One particularly suitable techni-
que 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, zinc dichloride, etc.). 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 Encyclo-
pedia of Chemical Technology", Second Edition, Vol. 1, pages
894-895, Interscience Pu~lishers, a division of John Wiley
and Company, N.Y., 1963. Other equally appropriate and
convenient techniques for attaching the hydrocarbon-based
group R to the aromatic moiety Ar will occur readily to
those skilled in the art.
- 14 -

As will be appreciated from inspection of Formula I the
amino phenols of this invention contain at least one of each
of the following substituents: a hydroxyl group, a R group
as defined above, and a primary amine group, -NH2. Each of
the foregoing groups must be attached to a carbDn atom which
is a part of an aromatic nucleus in the Ar moiety. They
need not, however, each be attached to the same aromatic
ring if more than one aromatic nucleus is present in the Ar
moiety.
In a preferred embodiment, the amino phenols of this
invention contain one each of the foregoing substituents
(i.e., a, b and c are each l) and but a single aromatic
ring, most preferably benzene. This preferred class of
amino phenols can be represented by the formula
OH
~ (NH2)1-2
R' ~ (R'')z Formula II
wherein the R' grollp is a substantially saturated hydro-
carbon-based group of about 30 to about 400 aliphatic carbon
atoms located ortho or para to the hydroxyl group, R" is a
lower alkyl, lower al~oxyl, nitro group or halogen atom and
z is 0 or l. Usually z is 0 and R' is a substantially
saturated, purely hydrocarbyl aliphatic group. Often it is
an alkyl or alkenyl group para to the -OH substituent.
Often there is but one amino group, -NH2 in these preferred
amino phenols but there can be two.
In a still more preferred embodiment of this invention,
the amino phenol is of the formula
OH
~ NH2
tR") ~ Formula III
R'
- 15 -

4~
wherein R' is derived from homopolymerized or interpoly-
merized C2-l0 l-olefins and has an average of from about 3
to about 400 aliphatic carbon atoms and R~ and z are as
defined above. Usually R' is derived from ethylene, pro-
pylene, butylene and mixtures thereof. Typically, it isderive~ from polymerized isobutene. Often R' has at least
about 50 aliphatic carbon atoms and z is 0.
The amino phenols of the present invention can be
prepared by a number of synthetic routes. These routes can
vary in the type reactions used and the sequence in which
they are employed. For example, an aromatic hydrocarbon,
such as benzene, can be alkylated with alkylating agent such
as a polymeric olefin to form an alkylated aromatic inter-
mediate. This intermediate can then be nitrated, for
example, to form polynitro intermediate. The polynitro
intermediate can in turn be reduced to a diamine, which can
then be diazotized and reacted with water to convert one of
the amino groups into a hydroxyl group and provide the
desired amino phenol. Alternatively, one of the nitro
groups in the polynitro intermediate can be converted to a
hydroxyl group through fusion with caustic to provide a
hydroxy-nitro alkylated aromatic which can then be reduced
to provide the desired amino phenol.
Another useful route to the amino phenols of this
invention involves the ~lkylation of a phenol with an ole-
finic alkylating agent to form an alkylated phenol. This
alkylated phenol can then be nitrated to form an inter-
mediate nitro phenol which can be converted to the desired
amino phenols by reducing at least some of the nitro
3~ groups to amino groups.
- 16 -

~ ~ 5
Techniques for alkylating phenols are well known to
those skilled in the art as the above-noted article in Kirk-
Othmer "Encyclopedia of Chemical Technology" demonstrates.
Techniques for nitrating phenols are also kn~wn. See, for
example, in Kirk-0thmer "Encyclopedia of Chemical Technology",
Second Edition, Vol. 13, the article entitled "Nitrophenols",
page 888 et seq., as well as the treatises "Aromatlc Substi-
tution; Nitration and ~alogenation" by P.B.D. De La Mare and
J.H. Ridd, N.Y., Academic Press, 1959: "Nitration and Aro-
matic Reactivity" by J.G. Hogget, London, Cambridge UniversityPress, 1961: and "The Chemistry of the Nitro and Nitroso
Groups", Henry Feuer, Editor, Interscience Publishers,
N.Y., 1969.
Aromatic hydroxy compounds can be nitrated with nitric
acid, mixtures of nitric acid with acids such as sulfuric
acid or boron trifluoride, nitrogen tetraoxide, nitronium
,.
tetrafluoroborates and acyl nitrates. Generally, nitric
acid of a conceDtration of, for example, about 30-90% is a
convenient nitrating reagent. Substantially inert liquid
:.
zo ~diluents and solvents such as acetic or butyric acid can aid
in carrying out the reaction by improving reagent contact.
Conditions and concentra~ions for nitrating hydroxy ~ -
aromatic~compounds~are~al~so well known~in ~the art. For
example, the reaction can be~carried out a~t temperature~ of
about -15 C. to about 150 C.~ Usua~lly nitration is con-
v-nlently ~arxled out~ betweeo about~25-75'C.
Generally,~depending on the particu]ar~nltrating agent -
about 0.5-4~moles~of.Ditrating~agent~is used~ for every mole
of aromatic nucleus present in the hydroxy aromatic inter- ;`
;mediate~to be nltrated~ If more than~one aromatic nucleus is
'; ' '`

t.~
present in the Ar moiety, the amount of nitrating agent can
be increased proportionately according to the number of such
nuclei present. For example, a mole of naphthalene-based
aromatic intermediate has,for purposes of this invention,
the equivalent of two "single ring" aromatic nuclei so that
about 1-4 moles of nitrating agent would generally be used.
When nitric acid is used as a nitrating agent usually about
1.0 to about 3.0 moles per mole of aromatic nucleus is used.
Up to about a 5-molar excess of nitrating agent (per "single
ring" aromatic nucleus) may be used when it is desired to
drive the reaction forward or carry it out rapidly.
Nitration of a hydroxy aromatic intermediate generally
takes 0.25 to 24 hours, though it may be convenient to react
the nitration mixture for longer periods, such as 96 hours.
Reduction of arom~ti~ nitro compounds to the corres-
ponding amines is also well known. See, for example, the
article entitled "Amination by Reduction" in Kirk-Othmer
"Encyclopedia of Chemical Technology", Second Edition, Vol.
2, pages 76-99. Generally, such reductions can be carried
out with, for example, hydrogen, carbon monoxide or hydra-
zine, (or mixtures of same) in the presence of metallic
catalysts such as palladium, platinum and its oxides,
nickel, copper chromite, etc. Co-catalysts such as alkali
or alkaline earth metal hydroxides or amines (including
amino phenols) can be used in these catalyzed reductions.
Reduction can also be accomplished through the use of
reducing metals in the presence of acids, such as hydro-
chloric acid. Typical reducing metals are zinc, iron and
tin; salts of these metals can also be used.
- 18 ~

Nitro groups can also be reduced in the Zinin reaction,
which is discussed in "Organic Reactions", Vol. 20, John
Wiley & Sons, N.Y., 1973, page 455 et seq. Generally, the
Zinin reaction involves red~ction of a nitro group with
divalent negative sulfur compounds, such as alkali metal
sulfides, polysulfides and hydrosulfides.
The nitro groups can be reduced by electrolytic action;
see, for example, the "Amination by Reduction" article,
referred to above.
Typically the amino phenols of this invention are
obtained by reduction of nitro phenols with hydrogen in the
presence of a metallic catalyst such as discussed above.
; This reduction is generally carried out at temperatures of
about 15 - 250 C., typically, about 50 -150 C., and hydrogen
pressures of about 0-2000 psig~ typically, about 50-250
psig. The reaction time for reduction usually varies
between about 0.5-50 hours. Substantially inert liquid
diluents and solvents, such as ethanol, cyclohexane, etc.,
can be used to facilitate the reaction. The amino phenol
product is obtained by well-~nown techniques such as dis-
tillation, filtration, extraction, and so forth.
The reduction is carried out until at least about 50%,
usually about 80%, of the nitro groups present in the nitro
~ntermediate mixture are converted to amino groups. The
typical route to the amino phenols of this invention just
described can be summarized as
, ~I) nitrating with at least one nitrating agent at
.~ lea~t one compound of the formula
. (OH~C
(R)a Ar' Form~la IV
-- 19 --

wher~in R is a substantially~u~a~te~ hydrocarbon-based
group of at least 10 aliphatic carbon atoms; a and c are
each independent~y an integer of 1 up to three times the
number of aromatic nuclei present in Ar with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of Ar'; and Ar' is an aromatic moiety having 0 to 3
optional substituents selected from the qroup consisting of
lower alkyl, lower alkoxyl, nitro, and halo, or combinations
of two or more optional substituents, with the provisos that
(a) Ar' has at least one hydrogen atom directly bonded to a
carbon atom which is part of an aromatic nucleus, and (b)
when Ar' is a benzene having only one hydroxyl and one R
substituent, the R substituent is ortho or para to said
hydroxyl substituent, to form a first reaction mixture
containing a nitro intermediate, and (II) reducing at least
about 50% of the nitro groups in said first reaction mixture - -
to amino groups.
Usually this means reducing at least about 50% of the
nitro groups to amino groups in a compound or mixture of
compounds of the formula
(OlH)c
(R)a Ar (NO2) Formula V
wherein R is a substantially saturated hydrocarbon-based
substituent of at least 10 aliphatic carbon atoms; a, b and
c are each independently an integer of 1 up to three times
the number of aromatic nuclei present in Ar with the pro-
viso that the sum of a, b and c does not exceed the
unsatisfied valences.of Ar: and Ar is an aromatic moiety
having 0 to 3 optional substituents selected from the group
consisting of lower alkyl, lower alkoxyl, halo, or combina-
- 20 -

tions of two or more of said optional substit~ents: with the
proviso that when Ar is a benzene nucleus having only one
hydroxyl and one R substituent, the R substituent is ortho
or para to said hydroxyl substituent.
(B) The Deterqent/Dispersants
In general the detergent/dispersants (B) used in the
combinations of this invention are materials known to those
skilled in the art and they have been described in numerous
boo~s, articles and patents. A number of these are noted
hereinbelow in relation to specific types of detergent/
dispersants.
(B)(I) The Neutral or Basic Metal Salts of Orqanic
Sulfur Acids, CarboxYlic Acids or Phenols --
The choice of metal used to maXe these salts is us~ally
not critical and therefore virtually any metal can be used.
For reasons of availability, cost and maximum effectiveness,
certain metals are more commonly used. These include the
alkali and alkaline earth metals (i.e., the Group IA and IIA
metals excluding francium and radium). Group IIB metals as
well as polyvalent metals such as aluminum, chromium, molyb-
denum, wolfram, manganese, iron, coba~t, nic~el, and copper
can also be used. Salts containing a mixture of ions of two
or more of these metals are often used.
These salts can be neutral or basic. The former con-
tain an amo~int of metal cation just sufficient to neutralize
the acidic groups present in salt anion; the former contain
~ an excess of metal cation and are often termed overbased,
; hyperbased or superbased salts.
- 21 -

S
These basic and neutral salts can be of oil-soluble
organic sulfur acids such as sulfonic, sulfamic, thiosul-
fonic, sulfinic, sulfenic, partial ester sulfuric, sulfurous
and thiosulfuric acid. Generally they are salts of carbo-
cyclic or aliphatic sulfonic acids.
The carbocyclic sulfonic acids include the mono- or
poly-nuclear aromatic or cycloaliphatic compounds. The oil-
soluble sulfonates can be represented for the most part by
the following formulae:
[Rx- T -(SO3)y]zMb Formula VI
lR'- (S3 ) a]d ~ Formula VII
; In the above formulae, M is either a metal cation as des-
cribed hereinabove or hydrogen; T is a cyclic nucleus such
as, for example, benzene, naphthalene, anthracene, phenan-
` 15 threne, diphenylene oxide, thianthrene, phenothioxine,
I diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl
; sulfide, diphenylamine, cyclohexane, petroleum naphthenes,
decahydro-naphthalene, cyclopentane, etc.; R in Formula VI
is an aliphatic group such as alkyl, alkenyl, alkoxy,
alkoxyalkyl, carboalkoxyalkyl, etc.; x is at least 1, and
x + T contains a total of at least about 15 carbon atoms.
R' in Formula VII is an aliphatic radical containing at
least about 15 carbon atoms and M is either a metal cation
or hydrogen. Examples of types of the R' radical are alkyl,
alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific
examples of R' are groups deri~ed from petrolatum, satu-
rated and un~aturated para$fin wax, and polyolefins, in-
cluding polymerized C2 ~ C3, C4, C5 ~ C6 ~ etc., olefins
containing from about 15 to 7000 or more carbon atoms. ~he
- 22 -
~,'' "''.'. `,.

lVt~ S
groups T, R, and R' in the above formulae can also contain
other inorganic or organic substituents in addition to those
enumerated above such as, for example, hydroxy, mercapto,
halogen, nitro, amino, nitroso, sulfide, disulfide, etc. In
Formula VI, x, y, z and b are at least 1, and likewise in
Formula VII, a, b and d are at least 1.
The following are specific examples of oil-soluble
sulfonic acids coming within the scope of Formulae I and II
above, and it is to be understood that such examples serve
also to illustrate the salts of such sulfonic acids useful
in this invention. In other words, for every sulfonic acid
enumerated it is intended that the corresponding neutral and
basic metal salts thereof are also understood to be illus-
trated. Such sulfonic acids are mahogany sulfonic acids;
bright stock sulfonic acids; sulfonic acids derived from
lubricatin~ oil fractions having a Saybolt viscosity from
about 100 seconds at 100F. to about 200 seconds at 210F.;
petrolatum sulfonic acids; mono- and poly-wax substituted
sulfonic and polysulfonic acids of, e.g., benzene, naphtha-
lene, phenol, diphenyl ether, naphthalene disulfide, di-
phenylamine, thiophene, alpha-chloronaphthalene, etc.; other
substituted sulfonic acids such as alkyl benzene sulfonic
acids (where the alkyl group has at least 8 carbons), cetyl-
phenol mono-sulfide sulfonic acid9, dicetyl thianthrene
disulfonic acids, dilauryl beta naphthyl sulfonic acids,
dicapryl nitronaphthalene sulfonic acids, and alkaryl sul-
fonic acids such as dodecyl benzene "bottoms" sulfonic
acids.
The latter are acids derived from benzene which has
been alkylated with propylene tetramers or isobutene trimers
- 23 -

't~ ~
to introduce 1, 2, 3, or more branched-c~lain Cl~ substi-
tuents on the benzene rinq. Dodecyl benzene bottoms,
principally mixtures of mono- and di-dodecyl benzenes, are
available as by-products from the manufacture of household
- detergents. Similar products obtained from alkylation
bottoms formed during manufacture of linear alkyl sulfonates
(LAS) are also useful in makin~ the sulfonates used in this
invention
The production of sulfonates from detergent manufacture
by-products by reaction with, e.g., SO3, is well known to
those skilled in the art. See, for example, the article
"Sulfonates" in Kirk-Othmer "Encyclopedia of Chemical Techno-
logy", Second EditiOn, Vol. 19, pp. 291 et seq. published by
J,ohn wiley & Sons, N.Y. (1969).
Other descriptions of neutral and basic sulfonate salts
and techniques for making them can be found in the following
U.S. Patents: 2,174,110; 2,174,506; 2,174,508; 2,193,824;
2,197,800; 2,202,781; 2,212,786; 2,213,360; 2,228,598;
2,233,676; 2,239,974; 2,263,312; 2,276,090: 2,276,097;
2,315,514; 2,319,121; 2,321,022; 2,333,568; 2,333,788:
2,335,25~: 2,337,552; 2,346,568; 2,366,027; 2,374,193;
2,383,319; 3,312,618; 3,471,403; 3,488,284; 3,595,790; and
3,798,012.
Also included are aliphatic sulfonic acids such as
paraffin wax sulfonic acids, unsaturated paraffin wax
sulfonic acids, hydroxy-su~stituted paraffin wax sulfonic
acids, hexapropylene sulfonic acids, tetra-amylene sulfonic
acids,polyisobutene sulfonic acids wherein the polyiso-
butene contains from 20 to 7000 or more carbon atoms,
_ 24 -

chloro-substituted paraffin wax sulfonic acids, nitro-
paraffin wax sulfonic acids, etc.; cycloaliphatic sulfonic
acids such as petroleum naphthene sulfonic acids, cetyl
cyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic
acids, bis-(di-isobutyl) cyclohexyl sulfonic acids, mono- or
poly-wax substituted cyclohexyl sulfonic acids, etc.
With respect to the sulfonic acids or salts thereof
described herein and in the appended claims, it is intended
herein to employ the term "petroleum sulfonic acids" or
"petroleum sulfonates" to cover all sulfonic acids or the
salts thereof derived from petroleum products. A parti-
cularly valuable group of petroleum sulfonic acids are the
mahogany sulfonic acids (so called because of their reddish-
brown color) obtained as a by-product from the manufacture
of petroleum white oils by a sulfuric acid process.
Generally Group IA, IIA and IIB neutral and basic salts
of the above-described synthetic and petroleum sulfonic
acids are useful in the practice of this invention.
The carboxylic acids from which suitable neutral and
basic salts for use in this invention can be made include
aliphatic, cycloaliphatic, and aromatic mono- and polybasic
carboxylic acids such as the naphthenic acids, alkyl- or
alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-
substituted cyclohexanoic acids, alkyl- or alkenyl-sub-
stituted aromatic carboxylic acids. The aliphatic acids
generally contain at least eight carbon atoms and preferably
at least twelve carbon atoms. Usually they have no more
than about 400 carbon atoms. Generally, if the aliphatic
carbon chain is branched, the acids are more oil-soluble for
any given carbon atoms content.` The cycloaliphatic and

l~J~
aliphatic carboxylic acids can be saturated or unsaturated.
Specific examples include 2-ethylhexanoic acid, ~-linolenic
acid, propylene-tetramer-substituted maleic acid, behenic
acid, isostearic acid, pelargonic acid, capric acid, palmi-
toleic acid, linoleic acid, lauric acid, oleic acid, ricin-
oleic acid, undecylic acid, dioctylcyclopentane carboxylic
acid, myristic acid, dilauryldecahydronaphthalene carboxylic
acid, stearyl-octahydroindene carboxylic acid, palmitic
acid, commercially available mixtures of two or more car-
boxylic acids such as tall oil acids, rosein acids, and the
like.
A preferred group of oil-soluble carboxylic acids
useful in preparing the salts used in the present invention
are the oil-soluble aromatic carboxylic acids. These acids
are represented by the general formula:
X \
(R*)a (Ar*)- -C-XH) m Formula VIII
where R* is an aliphatic hydrocarbon-based group of at least
four carbon atoms, and no more than about 400 aliphatic
carbon atoms, a is an integer of from one to four, Ar* is a
: 20 polyvalent aromatic hydrocarbon nucleus of up to about 14
carbon atoms each X is independently a sulfur or oxygen
atom, and m is an integer of from one to four with the
proviso that R* and a are such that there is an average of
at least 8 aliphatic carbon atoms provided by the R* groups
for each acid molecule represented by Formula VIII. Examples
of aromatic nuclei represented by the variable Ar* are the
polyvalent aromatic radicals derived from benzene, naphtha-
lene, anthracene, phenanthrene, indene, fluorene, biphenyl,
and the like. Generally, the radical represented by Ar*
will be a polyvalent nucleus derived from benzene or naphtha-
- 26 -

lV~
lene such as phenylenes and naphthylene, e.g., methylphenyl-
enes, ethoxyphenylenes, nitrophenylenes, isopropylphenylenes,
hydroxyphenylenes, mercaptophenylenes, N,N-diethylamino-
phenylenes, chlorophenylenes, dipropoxynaphthylenes, tri-
ethylnaphthylenes, and similar tri-, tetra-, pentavalent
nuclei thereof, etc.
The ~* groups are usually purely hydrocarbyl groups,
preferably groups such as alkyl or alkenyl radicals.
However, the R* groups can contain small number substituents
such as phenyl, cycloalkyl (e.g., cyclohexyl, cyclopentyl,
etc.) and nonhydrocarbon groups such as nitro, amino, halo
(e.g., chloro, bromo, etc.), lower alkoxy, lower alkyl
mercapto, oxo substituents (i.e.,=O), thio groups (i.e.,
=S), interrupting groups such as -NH-, -O-, -S-, and the
like provided the essentially hydrocarbon character of the
R* group is retained. The hydrocarbon character is retained
for purposes of this invention so long as any non-carbon
atoms present in the R* groups do not account for more than
about 10% of the total weight of the R* groups.
Examples of R* groups include butyl, isobutyl, pel~tyl,
octyl, nonyl, dodecyl, docosyl, tetracontyl, S-chlorohexyl,
4-ethoxypentyl, 4-hexenyl, 3-cyclohexyloctyl, 4-(p-chloro-
phenyl)-octyl, 2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl,
and substituents derived from polymerized olefins such as
polychloroprenes, polyethylenes, polypropylenes, polyiso-
butylenes, ethylene-propylene copolymers, chlorinated
olefin polymers, oxidized ethylene-propylene copolymers, and
the like. Likewise, the group Ar* may contain non-hydro-
carbon substituents, for example, such diverse substituents
as lower alkoxy, lower alkyl mercapto, nitro, halo, alkyl or
- 27 -

lu~
alkenyl groups of less than four carbon atoms, hydroxy,
mercapto, and the like.
A group of particularly useful carboxylic acids are
those of the formula:
/X
/ ~ C XH) m
R* ~ Ar* ~ Formula IX
~ ~ (XH)p
where R*, X, Ar*, m and a are as defined in Formula VIII and
p is an integer of 1 to 4, usually 1 or 2. Within this
group, an especially preferred class of oil-soluble car-
boxylic acids are those of the formula:
(R**) ~ C~~) b Formula X
--~ OH )C
where R** in Formula X is an aliphatic hydrocarbon group
containing at least 4 to about 400 carbon atoms, a is an
integer of from 1 to 3, b is 1 or 2, c is zero, 1, or 2 and
preferably 1 with the proviso that R** and a are such that
the acid molecules contain at least an average of about
twelve aliphatic carbon atoms in the aliphatic hydrocarbon
substituents per acid molecule. And within this latter
group of oil-soluble carboxylic acids, the aliphatic-hydro-
carbon substituted salicylic acids wherein each aliphatic
2~ hydrocarbon substituent contains an average of at least
: about sixteen carbon atoms per substituent and one to three
substituents per molecule are particularly useful. Salts
- 28 -

lt~
prepared from such salicylic acids wherein the ali~hatic
hydrocarbon substituents are derived from polymerized
olefins, particularly polymerized lower l-mono-olefins such
as polyethylene, polypropylene, polisobutylene, ethylene/
propylene copolymers and the like and having average carbon
contents of about 30 to about 400 carbon atoms.
The carboxylic acids corresponding to Formulae vIII-rx
above are wellknown or can be prepared according to proce-
dures known in the art. Carboxylic acids of the type
illustrated by the above formulae and processes for pre-
paring their neutral and basic metal salts are well known
and disclosed, for example, in such U.S. Patents as 2,197,832;
2,197,835; 2,252,662; 2,252,664; 2,714,092: 3,410,798 and
3,595,791.
Another type of neutral and basic carboxylate salt used
in this invention are those derived from alkenyl succinates
of the general formula
R* - CHCOOH Formula XI
CH2COOH
wherein R* is as defined above in Formula VIII. Such salts
and means for making them are set forth in U.S. Patents
3,271,130: 3,567,637 and 3,632,510.
Other patents specifically describing techniques for
maXin~ basic salts of the hereinabove-described sulfonic
acids, carboxylic acids, and mixtures of any two or more of
these include U.S. Patent Nos. 2,501,731: 2,616,904; 2,616,905;
2,61~,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049:
2,777,874: 3,027,325: 3,256,186; 3,282,835; 3,384,585;
3,373,10B: 3,365,396: 3,342,733: 3,320,162; 3,312,618:
- 29 -

lV~ S
3,318,809: 3,471,401; 3,488,284: 3,595,790, and 3,629,109.
Neutral and basic salts of phenols (generally known as
phenates) are also useful in the compositions of this inven-
tion and well known to those skilled in the art. The
phenols from which these phenates are formed are of the
general formula
(R*)n (Ar*) (XH)m Formula XII
wherein R*, n, Ar*, X and m have the same meaning and
preferences as described hereinabove with reference to
Formula VIII. The same examples described with respect to
Formula VIII also apply.
A commonly available class of phenates are those made
from phenols of the general formula
(R') ~ (OH)b Formula XIII
(R4)z
wherein a i8 an integer of 1-3, b is of 1 or 2, z i8 0 or 1,
R' in Formula XIII is a substantially saturated hydrocarbon-
based substituent having an average of from 30 to about 400
aliphatic carbon atoms and R is selected from the group
consisting of lower alkyl, lower alkoxyl, nitro, and halo
groups.
One particular class of phenates for use in this inven-
tion are the basic (i.e., overbased, etc.) Group IIA metal
~- sulfurized phenates made by sulfurizing a phenol as des-
i~ :
.. .. .
,~ ..
~ - 30 -

t~ ~ ~
cribed hereinabove with a sulfurizinq agent such as sulfur,
a sulfur halide, or sulfide or hydrosulfide salt. Techni-
ques for making these sulfurized phenates are described in
U.S. Patents 2,680,096, 3,036,971 and 3,775,321.
Other phenates that are useful are those that are made
from phenols that have been linked through alkylene (e.~.,
methylene) bridges. These are made by reacting single or
multi-ring phenols with aldehydes or ketones, typically, in
the presence of an acid or basic catalyst. Such linked
phenates as well as sulfurized phenates are described in
detail in U.S. Patent 3,350,038; particularly columns 6-8
thereof.
Naturally, mixtures of two or more neutral and basic
salts of thehereinabove described organic sulfur acid,
; carboxylic acids and phenols can be used in the compositions
of this invention. usually the neutral and basic salts will
be sodium, lithium, magnesium, calcium, or barium salts
including mixtures of two or more of any of these.
(B)(II) The HYdrocarbYl-Substituted Amine
The hydrocarbyl-substituted amines used in making the
compositions of this invention are well Xnown to those of
skill in the art and they are described in a number of
patents. Among these are U.S. Patents 3,275,554: 3,438,757,
3,454,555; 3,565,804; 3,755,433, and 3,822,209.
`::
., ~
.~:
'
- 31 -

A typical hydrocarbyl amine has the general formula:
([AXN]X[-N([ UN ]a[ ~ N-]b)]y)R CHI+2y+ay-c
Formula XIV
wherein A is hydrogen, a hydrocarbyl group of from 1 to 10
carbon atoms, or hydroxyhydrocarbyl group of from 1 to 10
carbon atoms; X is hydrogen, a hydrocarbyl group of from 1
to 10 carbon atoms, or hydroxyhydrocarbyl group of from 1 to
10 carbon atoms, and may be taken together with A to form a
ring of from 5 to 6 annular members and up to 12 carbon
atoms; U is an alkylene group of from 2 to 10 carbon atoms,
R2 is an aliphatic hydrocarbon group of from about 30 to 400
carbon atoms; a is an integer of from 0 to 10; b is an
integer of from 0 to 1; a+2b is an integer of from 1 to 10;
c is an integer of from 1 to 5 and is as an average in the
~:! range of 1 to 4, and equal to or less than the number of
lS nitrogen atoms in the molecule; x is an integer of from 0 to
; y i8 an integer of from 0 to 1; and x+y is equal to 1.
In interpreting this formula, it is to be understood
that the R2 and H atoms are attached to the unsatisfied ~;
nitrogen valences within the brackets of the formula. Thus, -
for example, the formula includes subgeneric formulae where-
in the R2 is attached to terminal nitrogens and isomeric
subgeneric formula wherein it is attached to non-terminal
nitrogen atoms. Nitrogen atoms not attached to an R2 may
bear a hydrogen or an AXN substituent.
The hydrocarbyl amines useful in this invention and
i~ embraced by the above formula include monoamines of the
general formula
AXNR2 . Formula XV
- 32 -

Illustrative of such monoamines are the following:
poly(propylene)amine
N,N-dimethyl-N-poly(ethylene/propylene)amine
(50:50 mole ratio of monomers)
poly(isobutene)amine
N,N-di(hydroxyethyl)-N-poly(isobutene)amine
poly(isobutene/l-butene/2-butene)amine
(50:25:25 mole ratio of monomer)
N-(2-hydroxypropyl)-N-poly(isobutene)amine
N-poly(l-butene)-aniline
N-poly(isobutene)-morpholine
Among the hydrocarbyl amines embraced by the general
Formula XIV as set forth above, are polyamines of the
general formula
-N(t-uN-la~-uN ~ ]b)R c~2y+ay-c Formula XVI
'
Illu~trative of such polyamines are the following:
N-poly(isobutene) ethylene diamine
N-poly(propylene) trimethylene diamine
N-poly(l-butene) diethylene triamine ;" .
N',N'-poly(isobutene) tetraethylene pentamine
N,N-dimethyl-N'-poly(propylene),1,3-propylene
diamine
The hydrocarbyl sub~tituted amine~ useful in forming
!:; the compositions in this invention include certain N-amino-
~i~ 25 hydrocarbyl morpholines which are not embraced in the
general Formula XIV above. These hydrocarbyl-substituted `"
aminohydrocarbyl morphoIines have the general formula:
; R2 NU- ~ Formula XVII
t~ A
,
,,~ - 33 -

~ 3~
wherein R2 is an aliphatic hydrocarbon group of from about
30 to about 400 carbons, A is hydrogen, hydrocarbyl of from
1 to 10 carbon atoms or hydroxy hydrocarbyl group of from 1
to 10 carbon atoms and U is an alkylene group of from 2 to
10 carbon atoms. These hydrocarbyl-substituted aminohydro-
carbyl morpholines as well as the polyamines described by
Formula XV are among the typical hydrocarbyl-substituted
amines used in preparing compositions of this invention.
(B)(III) The Acylated Nitrogen-containing Compounds
A number of acylated, nitrogen-containing compounds
having a substituent of at least 10 aliphatic carbon atoms
and made by reacting a carboxylic acid acylating agent with
an amino compound are known to those skilled in the art. In
i such compositions the acylating agent is linked to the amino
compound through an imido, amido, amidine or acyloxy ammonium
linkage. The substituent of 10 aliphatic carbon atoms may
be in either the carboxylic acid acylating agent derived
portion of the molecule or in the amino compound derived
portion of the molecule. Preferably, however, it is in the
acylating agent portion. The acylating agent can vary from
formic acid and its acylating derivatives to acylating
agents having high molecular weight aliphatic substituents
of up to 5,000, 10,000 or 20,000 carbon atoms. The amino
compounds can vary from ammonia itself to amines having
aliphatic substituents of up to about 30 carbon atoms.
A typical class of acylated amino compounds useful in
making the compositions of this invention are those made by
reacting an acylating agent having an aliphatic substituent
of at least 10 carbon atoms and a nitrogen compound charac-
~ 30 terized by the presence of at least one -N~ group. Typi-
J
I
- 34 -

1'~ 5
cally, the acylating agent will be a mono- or polycarboxylic
acid (or reactive equivalent thereof) such as a substituted
succinic or propionic acid and the amino compound will be a
polyamine or mixture of polyamines, most typically, a mix-
ture of ethylene polyamines. The aliphatic substituent in
such acylating agents is often of at least about 50 and up
to about 400 carbon atoms. Usually it belongs to the same
generic class as the R' group of the amino phenols (A) and
therefore the preferences, examples and limitations dis-
cussed hereinabove relating to R' apply equally to this
aliphatic substituent. Exemplary of amino compounds useful
in making these acylated compounds are the following:
(1) polyalkylene polyamines of the general formula
R'''- N ( U-NI-t-nR~'' Formula XVIII
R''' R" '
wherein each R''' is independently a hyd~ogen atom or a C~-~2
hydrocarbon-based group, with proviso that at least one R is
a hydrogen atom, n is a whole number of 1 to 10 and U is a
C2-10 alkylene group, (2) heterocyclic-substituted polyamines
of the formula
R''' N-~-U N ~ U N ~ U2Y Formula XIX
R''' R'''
wherein R''' and U are as defined hereinabove, m is 0 or a
whole number of 1 to 10, m' is a whole number of 1 to 10 and
Y is an oxygen or divalent sulfur atom or a ~N-R''' group
and (3) aromatic polyamines of the general formula
Ar~NR''' 2 ) y Formula XX
wherein Ar is an aromatic nucleus of 6 to about 20 carbon
i
atoms, each R''' is as defined hereinabove and y is 2 to
- 35 -

about 8. Specific examples of the polyalkylene polyamines
(1) are ethylene diamine, tetra(ethylene)pentamine, tri-
(trimethylene)tetramine, 1,2-propylene diamine, etc.
Specific examples of the heterocyclic-substituted polyamines
(2) are N-2-aminoethyl piperazine, N-2 and N-3 amino propyl
morpholine, N-3-(dimethyl amino) propyl piperazine, etc.
Specific examples of the aromatic polyamines (3) are the
various isomeric phenylene diamines, the various isomeric
naphthylene diamines, etc.
Many patents have been described useful acylated nitrogen
compounds including U.S. Patents 3,172,892; 3,219,666:
3,272,746: 3,310,492; 3,341,542; 3,444,170; 3,455,831;
3,455,~32, 3,576,743; 3,630,904; 3,632,511, and 3,804,763.
A typical acylated nitrogen-containing compound of this
class is that made by reacting a poly(isobutene)-substituted
succinic anhydride acylating agent (e.g., anhydride~ acid,
ester, etc.) wherein the poly(isobutene) substitutent has
between about 50 to about 400 carbon atoms with a mixture of
ehtylene polyamines having 3 to about 7 amino nitrogen atoms
per ethylene polyamine and about 1 to about 6 ethylene units
made from condensation of ammonia with ethylene chloride.
In view of the extensive disclosure of this type of acylated
amino compound, further discussion of their nature and
; method of preparation is not needed here.
Another type of acylated nitrogen compound belonging to
this class is that made by reacting the afore-described
,~
~ . ,
- 36 -

alkylene amines with the afore-described substituted succinic
acids or anhydrides and aliphatic mono-carboxylic acids
having from 2 to about 22 carbon atoms. In these types of
acylated nitrogen compounds, the mole ratio of succinic acid
to mono-carboxylic acid ranges from about 1:0.1 to about
1:1. Typical of the mono-carboxylic acid are formic acid,
acetic acid, dodecanoic acid, butanoic acid, oleic acid,
stearic acid, the commercial mixture of stearic acid isomers
known as isostearic acid, tolyl acid, etc. Such materials
are more fully described in U.S. Patents 3,216,936 and
3,250,71S.
Still another type of acylated nitrogen compound useful
in making the compositions of this invention is the product
of the reaction of a fatty monocarboxylic acid of about 12-
30 carbon atoms and the afore-described alkylene amines,
typically, ethylene, propylene or trimethylene polyamines
containing 2 to 8 amino groups and mixtures thereof. The
fatty monocarboxylic acids are generally mixtures of straight
and branched chain fatty carboxylic acids containing 12-30
carbon atoms. A widely used type of acylated nitrogen
compound is made by reacting the afore-described alkylene
polyamines with a mixture of fatty acids having from 5 to
about 30 mole percent straight chain acid and about 70 to
about 95 percent mole branched chain fatty acids. Among the
commercially available mixtures are those known widely in
the trade as isostearic acid. These mixtures are produced
as a by-product from the dimerization of unsaturated fatty
acids as described ~n U.S. Patents 2,812,342 and 3,260,671.
- 37 -

1~'?~L~S
The branched chain fatty acids can also incl~de those
in which the branch is not alkyl in nature, such as found in
phenyl and cyclohexyl stearic acid and the chloro-stearic
acids. Branched chain fatty carboxylic acid/alkylene
polyamine products have been described extensively in the
art. See for example, U.S. Patents 3,110,673; 3,251,853;
3,326,801; 3,337,459; 3,405,064; 3,429,674; 3,468,639;
3,857,791.
(B)(IV) The Nitroqen-containinq Condensates of Phenols,
Aldehydes, and Amino Compounds
The phenol/aldehyde/amino compound condensates useful
in making the compositions of this invention include those
generically referred to as Mannich condensates. Generally
they are made by reacting simultaneously or sequentially at
least one active hydrogen compound such as hydrDcarbon-
substituted phenol (e.g., an alkyl phenol wherein the alkyl
group has at least about 30 up to about 400 carbon atoms),
having at least one hydrogen atom bonded to an aromatic
' carbon, with at least one aldehyde or aldehyde-producing
material (typically formaldehyde or formaldehyde precursor)
and at least one amino or polyamino compound having at least
one NH group,- The amino compounds include primary or
secondary mono-amines having hydrocarbon substituents of 1
to 30 car~on atoms or hydroxyl-substituted hydrocarbon
,. ~
`~ substituents of 1 to about 30 carbon atoms. Another type of
typical amino compound are the polyamines described during
~ the discussion of the acylated nitrogen-containing com-
J pounds.
r
~ 38 ~

lV~
Exemplary mono-amines include methyl ethyl amine,
methyl octadecyl amine, aniline, diethyl amine, diethanol
amine, dipropyl amine and so forth. The following U.S
Patents contain extensive descriptions of Mannich conden- -
sates which can be used in making the compositions of this
invention:
U.S. Patents
2,459,112 3,413,347 3,558,743
2,962,442 3,442,808 3,586,629
2,984,550 3,448,047 3,591,598
3,036,003 3,454,497 3,600,372
3,166,516 3,459,661 3,634,515
3,236,770 3,461,172 3,649,229
3,355,270 3,493,520 3,697,574
3,368,972 3,539,633
Condensates made from sulfur-containing reactants can
! al80 be used in the compositions of the present invention.
Such sulfur-containing condensates are described in U.S.
Patent 3,368,972; 3,649,229: 3,600,372; 3,649,659; and
` 20 3,741,896. Generally the condensates used in making the com-
positions of the invention are made from a phenol bearing
an alkyl substituent of about 6 to about 400 carbon atoms,
mDre typically, 30 tD abDut 250 carbon atDms. These typical
, .
; - 3g -

10~845
condensates are made from formaldehyde or C2-7 aliphatic
aldehyde and an amino compound such as those used in making
the acylated nitrogen-containing compounds described under
(B)(III).
These preferred condensates are prepared by reacting
about one molar portion of phenolic compound with about 1 to
about 2 molar portions of aldehyde and about 1 to about 5
equivalent portions of amino compound (an equivalent of
amino compound is its molecular weiqht divided by the number
of =NH groups present). The conditions under which such
~ condensation reactions are carried out are well known to
- those skilled in the art as evidenced by the above-noted
patents. Therefore, these patents are also incorporated by
reference for their disclosures relating to reaction con- -
ditions.
A particularly preferred class of condensation products
for use in the present invention are those made by a "2-step
process". Briefly, these nitrogen-containing condensates
- are made by (1) reacting at least one hydroxy aromatic
compound containing an aliphatic-based or cycloaliphatic-
based substituent which has at least about 30 carbon atoms
and up to about 400 carbon atoms with a lower aliphatic
1 Cl-7 aldehyde or reversible polymer thereof in the presence
'b,; of an alkaline reagent, such as an alkali metal hydroxide,
at a temperature up to about 150C.: (2) substantially
neutralizing the intermediate reaction mixture thus formed;
and (3) reacting the neutralized intermediate with at least
one compound which contains an amino group having at least
one -NH group.
- 40 -

lQ8g845
More preferably, these 2-step condensates are made from
(a) phenols bearing a hydrocarbon-based substituent having
about 30 to about 250 carbon atoms, said substituent being
derived from a polymer of propylene, l-butene, 2-butene, or
isobutene and (b) formaldehyde, or reversible polymer there-
of, (e.g., trioxane, paraformaldehyde) or functional equiva-
lent thereof, (e.g., methylal) and (c) an alkylene polyamine
such as ethylene polyamines having between 2 and 10 nitrogen
atoms.
The following specific illustrative examples describe
how to make the amino phenols and detergent/dispersants
which comprise the compositions of this invention. In these ~- -
examples, as well as in this specification and the appended
claims, all percenta~ges, parts and ratios are by weight,
unless otherwise expressly stated to the contrary. Tempera-
tures are in degrees centigrade (C.) unless expressly
stated to the contrary.
EXAMPLE lA
A mixture of 4578 parts of a polyisobutene-substituted
phenol prepared by boron trifluoride-phenol catalyzed
alkylation of phenol with a polyisobutene having a number
average molecular weight of approximately 1000 ~vapor phase
osmometry), 3052 parts of diluent mineral oil and 725 parts
; of textile spirits is heated to 60 to achieve homogenity.
After cooling to 30, 319.5 p~rts~ of 16 molar nitric acid in
.
.
- 41 -

"` 101~845
600 parts of water is added to the mixture. Cooling is
nec-ssary to keep the mixture's temperature below 40.
After the reaction mixture is stirred for an additional two
hours, an aliquot of 3,710 parts is transferred to a second
reaction vessel. This second portion is treated with an
additional 127.B parts of 16 molar nitric acid in 130 parts
of water at 25-30. The reaction mixture is stirred for 1.5
hours and then stripped to 220/30 tor. Filtration provides
an oil solution of the desired intermediate (IA).
EXAMPLE lB
A mixture of 810 parts of the oil solution of the (IA)
intermediate described in Example lA, 405 parts of isopropyl
alcohol and 405 parts of toluene is charged to an appro-
priately sized autoclave. Platinum oxide catalyst (0.81
part) is added and the autoclave is evacuated and purged
with nitrogen four times to remove any résidual air.
Hydrogen is fed to the autoclave at a pressure of 29-55
psig while the content is stirred and heated to 27-92 for a
total of thirteen hours. Residual excess hydrogen is re-
moved from the reaction mixture by evacuation and purging
with nitrogen four times. The reaction mixture is then
' filtered through diatomaceous earth and the filtrate strip-
'~ ped to provide an oil solution of the desired amino phenol.
/ This solution contains 0.578% nitrogen.
,! 25 EXAMPLE 2
A mixture of 906 parts of an oil solution of an alkyl
phenyl sulfonic acid (having an average molecular weight of
450, vapor phase osmometry), 564 parts mineral oil, 600
parts toluene, 98.7 parts magnesium oxide and 120 parts
.
- 42 -

lOB~84 5
water is blown with carbon dioxide at a temperature of 78-
85 for seven hours at a rate of about 3 cubic feet of
carbon dioxide per hour. The reaction mixture is constantly
agitated throughout the carbonation. After carbonation, the
reaction mixture is stripped to 165/20 tor and the residue
filtered. The filtrate is an oil solution of the desired
overbased magnesium sulfonate having a metal ratio of about
3.
EXAMPLE 3
A polyisobutenyl succinic anhydride is prepared by
reacting a chlorinated poly(isobutene) (having an average
chlorine content of 4.3~ and an average of 82 carbon atoms)
with maleic anhydride at about 200. The resulting poly-
isobutenyl succir.ic anhydride has a saponification number of
90~ To a mixture of 1,246 parts of this succinic anhydride
and 1000 parts of toluene there is added at 25 76.6 parts
of barium oxide. The mixture is heated to 115C. and 125
parts of water is added drop-wise over a period of one hour.
The mixture is then allowed to reflux at 150C. until all
the barium oxide is reacted. Stripping and filtration
provides a filtrate having a barium content of 4.71%.
EXAMPLE 4
A mixture of 1500 parts of chlorinated poly(isobutene)
(of molecular weight of about 950 and having a chlorine
content of 5.6%), 285 parts of an alkylene polyamine having
an average composition corresponding stoichiometrically to
tetraethylene pentamine and 1200 parts of benzene is heated
to reflux. The mixture's temperature is then slowly in-
creased over a 4-hour period to 170 while benzene is
removed. The cooled mixture is diluted with an equal volume
- 43 -

108g~45
of mixed hexanes and absolute ethanol (1:1). This mixture
is heated to reflux and a 1/3 volume of 10% aqueous sodium
carbonate is added to it. After stirring, the mixture is
allowed to cool and the phases separated. The organic phase
is washed with water and stripped to provide the desired
polyisobutenyl polyamine having a nitrogen content of 4.5%.
EXAMPLE 5
. .
A mixture of 140 parts of toluene and 400 parts of a
polyisobutenyl succinic anhydride (prepared from the poly-
(isobutene) having a molecular weight of about 850, vapor
phase osmometry) having a saponification number of 109 and
63.6 parts of an ethylene amine mixture having an average
composition corresponding in stoichiometry to tetraethylene
pentamine, is heated to 150C. while the water~toluene
azeotrope is removed. The reaction mixture is then heated
to 150C under reduced pressure until toluene ceases to
distill. The residual acylated polyamine has a nitrogen
content of 4.7%.
EXAMPLE 6
To 1,133 parts of commercial diethylene triamine heated
at 110-150 is slowly added 6820 parts of isostearic acid
over a period of two hours. The mixture is held at 150 for
one hour and then heated to 180 over an additional hour.
Finally, the mixture is heated to 205 over O.S hour;
throughout this heating, the mixture is blown with nitrogen
to remove volatiles. The mixture is held at 205-230 for a
total of ll.S hours and then stripped at 230/20 tor to
provide the desired acylated polyamine as a residue con-
taining 6.2% nitrogen.
- 44 -

108g845
EXAMPLE 7
To a mixture of 50 parts of a polypropyl-substituted
phenol (having a molecular weight of about 900, vapor phase
osmometry), 500 parts of mineral oil (a solvent refined
paraffinic oil having a viscosity of 100 SUS at 100F.) and
130 parts of 9.5% aqueous dimethylamine solution (equivalent
to 12 parts amine) is added drop-wise, over an hour, 22
parts of a 37% aqueous solution of formaldehyde (corres-
ponding to a parts aldehyde). During the addition, the
reaction temperature is slowly increased to 100 and held at
that point for three hours while the mixture is blown with
nitrogen. To the cooled reaction mixture is added 100 parts
toluene and 50 parts mixed butyl alcohols. The organic
phase is washed three times with water until neutral to
litmus paper and the organic phase filtered and stripped to
200/5-10 tor. The residue is an oil solution of the final
product containing 0.45% nitrogen.
EXAMPLE 8
A mixture of 140 parts (by weight) of a mineral oil,
174 parts of a poly(isobutene) (molecular weight 1000)-sub-
stituted succinic anhydride having a saponification number
of 105 and 23 parts of isostearic acid is prepared at 90C.
To this mixture there is added 17.6 parts of a mixture of
polyalkylene amines having an overall composition corres-
ponding to that of tetraethylene pentamine at 80-100C.
throughout a period of 1.3 hours. The reaction is exothermic.
The mixture is blown at 225C. with nitrogen at a rate of 5
pounds per hour for 3 hours whereupon 47 parts of an aqueous
distillate is obtained. The mixture is dried at 225C. for
1 hour, cooled to 110C. and filtered to provide the desired
final product in oil solution.

108~845
The lubricating oils in which the nitrogen-containing
additive combinations of this invention are useful can be of
synthetic, animal, vegetable or mineral (e.g., petroleum)
origin. Ordinarily, mineral oils are used because of their
availability, general utility and low cost. In certain
applications oils belonging to one of the other three
classes may be used. For example, synthetic polyester oils
~e.g., didodecyl adipate and pentaerythritol tetracaprylate)
are often used, especially in jet engine lubrication.
Mixtures of oils within one of the four classes or between
such classes can often be used. Generally, the lubricating
oils used will be fluid oils ranging in viscosity from about
40 SUS (Saybolt Universal Seconds) at 37.5 to 200 SUS at
99. The additive combinations of this invention are nor-
mally used in an amount ranging from 0.5 to about 30 parts
by weight combination per hundred parts of oil.
This invention also contemplates the use of other
additives in the lubricating oil compositions of this inven-
tion. These other additives include such conventional
additive types as anti-oxidants, extreme pressure agents,
corrosion-inhibiting agents, pour point depressants, color
stabilizing agents, anti-foam agents, and other such addi-
tive materials known generally to those skilled in the art
of formulating lubricating oil compositions.
As noted hereinabove, the nitrogen-containing com-
positions of this invention are particularly useful in for-
mulating novel lubricating oils for use in two-cycle engines.
In general, the two-cycle engine lubricating oil composi-
tions of this invention contain about 98 to about 50% oil
or mixture of oils of lubricating viscosity. Typical composi-
- 46 -

4S
tions contain about 90 to about 60% oil. The presently
preferred oils are mineral oils and mineral oil-synthetic
polymer and/or synthetic ester oil mixtures. Polybutenes of
molecular weights of about 250 to about 1,000 (as measured
by vapor phase osmometry) and fatty acid ester oils of
polyols such as pentaerythritol and trimethylol propane are
typical synthetic oils used in preparing these two-cycle
oils.
These oil compositions contain about 2 to about 30~,
typically about 5 to about 20%, of at least one amino phenol
as described hereinabove and about 1 to about 30%, typically
2 to about 20% of at least one detergent/dispersant. The
ratio (by weight) of amino phenol to detergent/dispersant in
these oils varies between about 1:10 to about 10:1. Other
additives such as viscosity index (VI) improvers, lubricity
agents, anti-oxidants, coupling agents, pour point depres-
sing agents, extreme pressure agent, color stabilizers and
anti-foam agents can also be present.
Polymeric VI improvers have been and are being used as
bright stock replacement to improve lubricant film strength
and lubrication and/or to improve engine cleanliness. Dye
may be used for identification purposes and to indicate
whether a two-cycle fuel contains lubricant. Coupling
agents such as organic surfactants are incorporated into
some products t~ provide better component solubilities and
improved fuel/lubricant mix water tolerance.
Anti-wear and lubricity improvers, particularly sul-
furized sperm oil substitutes and other fatty acid and
vegetable oils, such as castor oil, are used in special
applications, such as racing and for very high fuel/lubri-
- 47 -

4S
cant ratios. Scavengers or combustion chamber deposit
modifiers are sometimes used to promote better spark plug
life and to remove carbon deposits. Halogenated compounds
and/or phosphorus- containing materials may be used for this
application.
Rust and corrosion inhibitors of all types are and may
be incorporated into two-cycle oil formulations. Odorants
or deodorants are sometimes used for aesthetic reasons.
Lubricity agents such as synthetic polymers (e.g.,
polyisobutene having a number average molecular weight in
the range of about 750 to about 15,000), as measured by
vapor phase osmometry or gel permeation chromatography,
polyol ether (e.g., poly(oxyethylene-oxypropylene)ethers)
and ester oils (e.g., the ester oils described above) can
also be used in the oil compositions of this invention.
Natural oil fractions such as bright stocks (the relatively
viscous products formed during conventional lubricating oil
manufacture from petroleum) can also be used for this
purpose. They are usually present in the two-cycle oil in
the amount of about 3 to about 20% of the total oil com-
position.
Diluents such as petroleum naphthas boiling at the
range of about 38-90 (e.g., Stoddard solvent) can also be
included in the oil compositions of this invention, typi-
cally in an amount of 5 to 25%.
Table 1 describes several illustrative two-cycle
engine oil lubricant compositions of this invention.

lU~'?t;~5
TABLE 1
TWO-CYCLE ENGINE OIL BLENDS
Amino2 Deter~ent-Dis~ersant2 Oil
Phenol of
Example Example 1 Example Amount Amount, pbw
A 6 2 2 92
B 3 2 1 96
C 10.6 6 2.1 87.3
D 7.5 4 3.5 89
E 6 3 2 92
F 15 5 3 82
.
I The same base oil is used in each blend; this oil is
a 650 neutral solvent extracted paraffinic oil cut with
20 percent by volume Stoddard solvent and containing 9
pbw per hundred parts of final blend of a bright stock
having a viscosity of 150 SUS at 100F.
2 Part by weight of the oil solution described in the
indicated Examples.
In some two-cycle engines the lubricating oil can be
directly injected into the combustion chamber along with the
fuel or into the fuel just prior to the time the fuel enters
the combustion chamber. The two-cycle lubricants of this
invention can be used in this type of engine.
As is well known to those skilled in the art, two-cycle
engine lubricating oils are often added directly to the fuel
to form a mixture of oil and fuel which is then introduced
into the engine cylinder. Such lubricant-fuel oil mixtures
are within the scope of this invention. Such lubricant-fuel
blends generally contain per 1 part of oil about 15-250
parts fuel, typically they contain 1 part oil to about 50-
100 parts fuel.
- 49 -

The fuels used in two-cycle engines are well known to
those skilled in the art and usually contain a major portion
of a normally liquid fuel such as hydrocarbonaceous petro-
leum distillate fuel (e.g., motor gasoline as defined by
ASTM Specification D-439-73). Such fuels can also contain
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. Examples of such fuel 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 60C. at the 10% distillation point to
about 205C. at the 90% distillation point.
Two-cycle fuels al80 contain 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), dyes, cetane improvers, anti-
oxidants such as 2,6-di-tertiary-butyl-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.
An example of a lubricant-fuel composition encompassed
by this invention is a blend of motor gasoline and the
lubricant blend described above in Example C in ratio (by
weight) of 50 parts gasoline to 1 part lubricant.
- 50 -

lV~
Concentrates containing the nitrogen-containing com-
positions of this invention are also within the scope of
this invention. These concentrates usually comprise about
20 to about 80% of one or more of the hereinabove described
oils and about 20 to about 80% of one or more nitrogen-
containing compositions. As will be readily understood by
those skilled in the art, such concentrates can also contain
one or more of the hereinabove described auxiliary additives
of various types. Illustrative of these inventive con-
centrates are the following:
EXAMPLE G
A concentrate for treating 2-cycle engine oils is
prepared by blending at room temperature 78.2 parts of the
oil solution described in Example 1 with 21.8 parts of the
oil solution described in Example 7.
EXAMPLE H
A concentrate for treating 2-cycle engine oils is
prepared by heating with mild agitation a mixture of 83.4
parts of the oil solution described in Example 1 with 16.6
parts of the oil solution described in Example 6 to 110
over a period of 0.5 hour.
-- 51 --