MULTIFUNCTIONAL VISCOSITY INDEX MODIFIER ADDITIVES DERIVED FROM AMIDO AMINES

ADDITIFS MULTIFONCTIONNELS MODIFIANT L'INDICE DE VISCOSITE, DERIVES D'AMIDOAMINES

English Abstract

ABSTRACT OF THE DISCLOSURE
The present invention is directed to a composition
of matter useful as a multifunctional viscosity
improver-dispersant for oleaginous compositions,
particularly lubricating oil compositions, comprising at
least one adduct or reaction product of (A) ethylene
copolymer, preferably ethylene propylene copolymer of at
least 15,000 number average molecular weight grafted with
monounsaturated mono- or dicarboxylic acid material; and
(B) amido-amine or thioamido-amine comprising reaction
product of at least one amine, preferably polyamine, and an
alpha, beta-unsaturated compound represented by the formula
<IMG>
wherein X is sulfur or oxygen, Y is -OR4, -SR4, or <IMG>
and R1, R2, R3, R4 and R5 are independently
selected from hydrogen, hydrocarbyl, and substituted
hydrocarbyl. The present invention is also directed to
oleaginous compositions and concentrates, particularly
lubricating oil compositions and concentrates, containing
said nitrogen containing carboxylic acid material grafted
high molecular weight ethylene copolymer adduct.

Claims

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THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An oil soluble composition of matter useful as
a multifunctional viscosity improver additive for
oleaginous composition comprising adduct of:
(A) high molecular weight ethylene copolymer
substituted carboxylic acid material comprising reaction
product of (i) ethylene copolymer having a number average
molecular weight of at least about 15,000, and (ii)
monounsaturated carboxylic acid material; and
(B) amido-amine or thioamido-amine comprising
reaction product of (i) polyamine, and (ii) alpha, beta-
unsaturated compound represented by the formula
<IMG>
wherein X is oxygen or sulfur, Y is -OR4, -5R4, or
<IMG> , and R1, R2, R3, R4 and R5 are
independently selected from hydrogen, hydrocarbyl, and
substituted hydrocarbyl.
2. The composition of matter according to claim 1
wherein said polyamine (B)(i) comprises polyamines
containing from 2 to about 60 carbon atoms and from 2 to
about 12 nitrogen atoms per molecule.
3. The composition of matter according to claim 2
wherein said polyamine (B)(i)comprises alkylenepolyamine or
polyalkylenepolyamine wherein each alkylene group contains
2 to 6 carbons and said alkylenepolyamine or polyalkylene-
polyamine contains from 2 to about 5 nitrogen atoms per
molecule.

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4. The composition of matter according to claim 1
wherein said monounsaturated carboxylic acid material
(A)(ii) is selected from the group consisting of C4 to
C10 monounsaturated dicarboxylic acid material, C3 to
C10 monounsaturated monocarboxylic acid material, and
mixtures thereof.
5. The composition of matter according to claim
4 wherein said adduct comprises (A), (B) and (C)
C12-C400 hydrocarbyl substituted dicarboxylic acid or
anhydride, or C50-C400 hydrocarbyl substituted
monocarboxylic acid.
6. The composition of matter according to claim
wherein said (C) is C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride.
7. The composition of matter according to claim
6 wherein said C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride is C12-C400 hydrocarbyl
substituted succinic acid or anhydride.
8. The composition of matter according to claim
7 wherein said C12-C400 hydrocarbyl substituted
succinic acid or anhydride is polyisobutylene succinic acid
or anhydride.
9. The composition of matter according to claim 4
wherein said monounsaturated carboxylic acid material (A)
(ii) comprises C4 to C10 monounsaturated dicarboxylic
acid material.
10. The composition of matter according to claim
9 wherein said C4 to C10 monounsaturated dicarboxylic
acid material is selected from the group consisting of
maleic anhydride, maleic acid, and mixtures thereof.

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11. The composition of matter according to claim
4 wherein said ethylene copolymer (A)(i) comprises
copolymer of ethylene and at least one C3 to C28
alpha-olefin.
12. The composition of matter according to claim
11 wherein said C3 to C28 alpha-olefin is propylene.
13. The composition of matter according to claim
11 wherein said adduct comprises (A), (B) and (C)
C12-C400 hydrocarbyl substituted dicarboxylic acid or
anhydride, or C50-C400 hydrocarbyl substituted
monocarboxylic acid.
14. The composition of matter according to claim
13 wherein said (C) is C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride.
15. The composition of matter according to claim
14 wherein said C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride is C12-C400 hydrocarbyl
substituted succinic acid or anhydride.
16. The composition of matter according to claim
wherein said C12-C400 hydrocarbyl substituted
succinic acid or anhydride is polyisobutylene succinic acid
or anhydride.
17. The-composition of matter according to claim
9 wherein said ethylene copolymer (A)(i) comprises a
copolymer of ethylene and at least one C3 to C28
alpha-olefin.
18. The composition of matter according to claim
17 wherein said C3 to C28 alpha-olefin is propylene.

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19. The composition of matter according to claim
wherein said ethylene copolymer (A)(i) comprises
copolymer of ethylene and at least one C3 to C28 alpha-
olefin.
20. The composition of matter according to claim
19 wherein said C3 to C28 alpha-olefin is propylene.
21. The composition of matter according to claim
4 wherein said monounsaturated dicarboxylic acid material
(A)(ii) comprises C3 to C10 monounsaturated mono-
carboxylic acid material.
22. The composition of matter according to claim
21 wherein said C3 to C10 monounsaturated monocar-
boxylic acid material is selected from the group consisting
of acrylic acid, acrylic ester, methacrylic acid,
methacrylic acid, and mixtures thereof.
23. The composition of matter according to claim
21 wherein said ethylene copolymer (A)(i) comprises a
copolymer of ethylene and at least one C3 to C28
alpha-olefin.
24. The composition of matter according to claim
15 wherein said C3 to C28 alpha-olefin is propylene.
25. The composition of matter according to claim
1 wherein said polyamine (B)(i) contains from 2 to about 60
carbon atoms and from 2 to about 12 nitrogen atoms, with at
least two of said nitrogen atoms being primary nitrogens,
and said alpha, beta-unsaturated compound (B)(ii)
comprising C1 to C4 alkyl esters of acrylic or
methacrylic acid.

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26. The composition of matter according to claim
wherein said ethylene copolymer (A)(i) comprises
ethylene-propylene copolymer.
27. The composition of matter according to claim
26 wherein said monounsaurated carboxylic acid material
(A)(ii) comprises maleic anhydride.
28. The composition of matter according to claim
27 comprising reaction product of (A), (B) and (C) C50 to
C400 polybutenyl substituted succinic anhydride.
29. The composition of matter according to claim
22 wherein said ethylene copolymer (A)(i) comprises
copolymer of ethylene and at least one C3 to C28
alpha-olefin.
30. The composition of matter according to claim
29 wherein said C3 to C28 alpha-olefin is propylene.
31. The composition of matter according to claim 1
wherein said ethylene copolymer (A)(i) comprises a co-
polymer of ethylene and at least one C3 to C28
alpha-olefin.
32. The composition of matter according to claim
31 wherein said C3 to C28 alpha-olefin is propylene.
33. The composition of matter according to claim 1
wherein said alpha-, beta-unsaturated compound (B)(ii)
comprises at least one member selected from the group
consisting of methyl acrylate, ethyl acrylate, propyl
acrylate, butyl acrylate, methyl methacrylate, ethyl
methacrylate, propyl methacrylate, and butyl methacrylate.

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34. The composition of matter according to claim
33 wherein said amine comprises alkylenepolyamine or
polyalkylene-polyamine wherein each alkylene group contains
2 to 6 carbons and said alkylenepolyamine
polyalkylenepolyamine contains from 2 to about 5 nitrogen
atoms per molecule.
35. The composition of matter according to claim
34 wherein said high molecular weight ethylene copolymer
substituted carboxylic acid material comprises at least one
of ethylene-propylene copolymer substituted with succinic
anhydride and ethylene-propylene copolymer substituted with
succinic acid, wherein said ethylene-propylene copolymer
has a number average molecular weight of at least about
15,000.
36. The composition of matter according to claim
wherein said polyamine (B)(i) comprises
ethylenepolyamine, propylenepolyamine, polyethylene-
polyamine, or polypropylenepolyamine.
37. The composition of matter according to claim
36 wherein said adduct comprises (A), (B) and (C)
C12-C400 hydrocarbyl substituted dicarboxylic acid or
anhydride, or C50-C400 hydrocarbyl substituted
monocarboxylic acid.
38. The composition of matter according to claim
37 wherein said (C) is C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride.
39. The composition of matter according to claim
38 wherein said C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride is C12-C400 hydrocarbyl
substituted succinic acid or anhydride.

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40. The composition of matter according to claim
39 wherein said C12-C400 hydrocarbyl substituted
succinic acid or anhydride is polyisobutylene succinic acid
or anhydride.
41. The composition of matter according to claim
34 wherein said high molecular weight ethylene copolymer
substituted carboxylic acid material comprises ethylene-
propylene copolymer substituted with propionic acid,
wherein said ethylene-propylene copolymer has a number
average molecular weight of at least about 15,000.
42. The composition of matter according to claim
41 wherein said polyamine (B)(i) comprises
ethylenepolyamine, propylenepolyamine, polyethylene-
polyamine or polypropylenepolyamine.
43. The composition of matter according to claim
wherein said polyamine (B)(i) contains an average of at
least 2 primary amine groups per molecule.
44. The composition of matter according to claim
43 wherein X of (B)(ii) is oxygen.
45. The composition of matter according to claim
44 wherein from about 3 to about 5 equivalents of said
polyamine, based on said primary amine content thereof, are
reacted per mole of said alpha, beta-unsaturated compound
(B) (ii).
46. The composition of matter according to claim
wherein said amido amine contains an average of from 1
to 3 amido groups per molecule.
47. The composition of matter according to claim
43 wherein X of (B)(ii) is sulfur.

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48. The composition of matter according to claim
47 wherein from about 3 to about 5 equivalents of said
polyamine, based on said primary amine content thereof, are
reacted per mole of said alpha, beta-unsaturated compound
(B)(ii).
49. The composition of matter according to claim
48 wherein said thioamido-amine contains an average of from
1 to 3 thioamido groups par molecule.
50. The composition of matter according to claim
41 wherein said polyamine (B)(i) contains at least 2
primary amine groups per molecule.
51. The composition of matter according to claim
50 wherein X of (B) (ii) is oxygen.
52. The composition of matter according to claim
51 wherein from about 3 to about 5 equivalents of said
polyamine (B)(i), based on said primary amine content
thereof, are reacted per mole of said alpha,
beta-unsaturated compound (B)(ii).
53. The composition of matter according to claim
52 wherein said amido-amine contains an average of from 1
to 3 amido groups per molecule.
54. The composition of matter according to claim
50 wherein X of (B)(ii) is sulfur.
55. The composition of matter according to claim
54 wherein from about 3 to about 5 equivalents of said
polyamine (B)(i), based on said primary amine content
thereof, are reacted per mole of said alpha,
beta-unsaturated compound (B)(ii).

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56. The composition of matter according to claim
wherein said thioamido-amine contains an average of from
1 to 3 thioamido groups per molecule.
57. The composition of matter according to claim 2
wherein said polyamine (B)(i) contains at least 2 primary
amine groups per molecule.
58. The composition of matter according to claim
57 wherein X of (B)(ii) is oxygen.
59. The composition of matter according to claim
58 wherein from about 3 to about 5 equivalents of said
polyamine (B)(i), based on said primary amine content
thereof, are reacted per mole of said alpha,
beta-unsaturated compound (B)(ii).
60. The composition of matter according to claim
59 wherein said amido amine contains an average of from 1
to 3 amido groups per molecule.
61. The composition of matter according to claim
57 wherein X of (B)(ii) is sulfur.
62. The composition of matter according to claim
61 wherein from about 3 to about 5 equivalents of said
polyamine (B)(i), based on said primary amine content
thereof, are reacted per mole of said alpha, beta-
unsaturated compound (B)(ii).
63. The composition of matter according to claim
62 wherein said thioamido-amine contains an average of from
1 to 3 thioamido groups per molecule.
64. An oleaginous composition exhibiting improved
viscometric properties and dispersancy comprising:

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(I) oleaginous material; and
(II) multifunctional viscosity improver-
dispersant additive comprising adduct of
(A) high molecular weight ethylene
copolymer substituted carboxylic acid
material comprising reaction product
of (i) ethylene copolymer having a
number average molecular weight of at
least about 15,000, and (ii)
monounsaturated carboxylic acid
material; and
(B) amido-amine or thioamido-amine
comprising reaction product of (i)
polyamine, and (ii) alpha, beta-
unsaturated compound represented by
the formula
<IMG>
wherein X is oxygen or sulfur, Y is
-OR4, -5R4, or
<IMG>, and R1, R2, R3, R4 and R5 are
independently selected from hydrogen,
hydrocarbyl, and substituted
hydrocarbyl.
65. The composition according to claim 64
containing a major amount of (I) and a minor amount of
(II).

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66. The composition according to claim 65 (I) is
a lubricating oil.
67. The composition according to claim 66 which
is a fully formulated lubricating oil composition.
68. The composition according to claim 66 which
contains from about 5 to about 49 wt. % of (II).
69. The composition according to claim 67
containing a viscosity improving and dispersant effective
amount of (II).
70. The composition according to claim 69
containing from about 0.01 to about 20 weight percent of
(II).
71. The composition according to claim 70
containing from about 0.1 to about 10 weight percent of
(II).
72. The composition according to claim 71
containing from about 0.2 to about 5 weight % of (II).
73. The composition according to claim 64 wherein
said polyamine (II)(B)(i) comprises polyamines containing
from 2 to about 60 carbon atoms and from 2 to about 12
nitrogen atoms per molecule.
74. The composition according to claim 73 wherein
said polyamine (II)(B)(i)comprises alkylenepolyamine or
polyalkylenepolyamine wherein each alkylene group contains
2 to 6 carbons and said alkylenepolyamine or
polyalkylenepolyamine contains from 2 to about 5 nitrogen
atoms per molecule.

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75. The composition according to claim 64 wherein
said monounsaturated carboxylic acid material (II)(A)(ii)
is selected from the group consisting of C4 to C10
monounsaturated dicarboxylic acid material, C3 to C10
monounsaturated monocarboxylic acid material, and mixtures
thereof.
76. The composition according to claim 75 wherein
said adduct (II) comprises (A), (B) and (C) C12-C400
hydrocarbyl substituted dicarboxylic acid or anhydride, or
C50-C400 hydrocarbyl substituted monocarboxylic acid.
77. The composition according to claim 76 wherein
said (C) is C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride.
78. The composition according to claim 77 wherein
said C12-C400 hydrocarbyl substituted dicarboxylic acid
or anhydride is C12-C400 hydrocarbyl substituted
succinic acid or anhydride.
79. The composition according to claim 78 wherein
said C12-C400 hydrocarbyl substituted succinic acid or
anhydride is polyisobutylene succinic acid or anhydride.
80. The composition according to claim 75 wherein
said monounsaturated carboxylic acid material comprises
C4 to C10 monounsaturated dicarboxylic acid material.
81. The composition according to claim 80 wherein
said C4 to C10 monounsaturated dicarboxylic acid
material is selected from the group consisting of maleic
anhydride, maleic acid, and mixtures thereof.
82. The composition according to claim 75 wherein
said ethylene copolymer (II)(A)(i) comprises copolymer of
ethylene and at least one C3 to C28 alpha-olefin.

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83. The composition according to claim 82 wherein
said C3 to C28 alpha-olefin is propylene.
84. The composition according to claim 80 wherein
said ethylene copolymer (II)(A)(i) comprises a copolymer of
ethylene and at least one C3 to C28 alpha-olefin.
85. The composition according to claim 84 wherein
said C3 to C28 alpha-olefin is propylene.
86. The composition according to claim 84 wherein
said adduct (II) comprises (A), (B) and (C) C12-C400
hydrocarbyl substituted dicarboxylic acid or anhydride, or
C50-C400 hydrocarbyl substituted monocarboxylic acid.
87. The composition according to claim 86 wherein
said (C) is C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride.
88. The composition according to claim 87 wherein
said C12-C400 hydrocarbyl substituted dicarboxylic acid
or anhydride is C12-C400 hydrocarbyl substituted
succinic acid or anhydride.
89. The composition according to claim 88 wherein
said C12-C400 hydrocarbyl substituted succinic acid or
anhydride is polyisobutylene succinic acid or anhydride.
90. The composition according to claim 81 wherein
said ethylene copolymer (II)(A)(i) comprises copolymer of
ethylene and at least one C3 to C28 alpha- olefin.
91. The composition according to claim 90 wherein
said C3 to C28 alpha-olefin is propylene.

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92. The composition according to claim 75 wherein
said monounsaturated dicarboxylic acid material (A)(ii)
comprises C3 to C10 monounsaturated mono- carboxylic
acid material.
93. The composition according to claim 92 wherein
said C3 to C10 monounsaturated monocarboxylic acid
material is selected from the group consisting of acrylic
acid, acrylic ester, methacrylic acid, methacrylic acid,
and mixtures thereof.
94. The composition according to claim 93 wherein
said ethylene copolymer (II)(A)(i) comprises a copolymer of
ethylene and at least one C3 to C28 alpha-olefin.
95. The composition according to claim 94 wherein
said C3 to C28 alpha-olefin is propylene.
96. The composition according to claim 94 wherein
said adduct (II) comprises (A), (B) and (c) C12-C400
hydrocarbyl substituted dicarboxylic acid or anhydride, or
C50-C400 hydrocarbyl substituted monocarboxylic acid.
97. The composition according to claim 96 wherein
said (C) is C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride.
98. The composition according to claim 97 wherein
said C12-C400 hydrocarbyl substituted dicarboxylic acid
or anhydride is C12-C400 hydrocarbyl substituted
succinic acid or anhydride.
99. The composition according to claim 98 wherein
said C12-C400 hydrocarbyl substituted succinic acid or
anhydride is polyisobutenylene succinic acid or anhydride.

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100. The composition according to claim 93
wherein said ethylene copolymer (II)(A)(i) comprises
copolymer of ethylene and at least one C3 to C28
alpha-olefin.
101. The composition according to claim 100
wherein said C3 to C28 alpha-olefin is propylene.
102. The composition according to claim 64 wherein
said ethylene copolymer (II)(A)(i) comprises a copolymer of
ethylene and at least one C3 to C28 alpha-olefin.
103. The composition according to claim 102
wherein said C3 to C28 alpha-olefin is propylene.
104. The composition according to claim 64 wherein
said alpha, beta-unsaturated compound (II)(B)(ii) comprises
at least one member selected from the group consisting of
methyl acrylate, ethyl acrylate, propyl acrylate, butyl
acrylate, methyl methacrylate, ethyl methacrylate, propyl
methacrylate, and butyl methacrylate.
105. The composition according to claim 104
wherein said polyamine (II)(8)(i) comprises
alkylenepolyamine or polyalkylenepolyamine wherein each
alkylene group contains 2 to 6 carbons and said
alkylenepolyamine or polyalkylenepolyamine contains from
about 5 to about 9 nitrogen atoms per molecule.
106. The composition according to claim 105
wherein said high molecular weight ethylene copolymer
substituted carboxylic acid material comprises at least one
of ethylene-propylene copolymer substituted with succinic
anhydride and ethylene-propylene copolymer substituted with
succinic acid, wherein said ethylene-propylene copolymer
has a number average molecular weight of at least about
15,000.

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107. The composition according to claim 106
wherein said polyamine (II)(B)(i) comprises
ethylenepolyamine, propylenepolyamine, polyethylene-
polyamine or polypropylenepolyamine.
108. The composition according to claim 105
wherein said high molecular weight ethylene copolymer
substituted carboxylic acid material comprises ethylene-
propylene copolymer substituted with propionic acid,
wherein said ethylene-propylene copolymer has a number
average molecular weight of at least about 15,000.
109. The composition according to claim 108
wherein said adduct (II) comprises (A), (B) and (C)
C12-C400 hydrocarbyl substituted dicarboxylic acid or
anhydride, or C50-C400 hydrocarbyl substituted
monocarboxylic acid.
110. The composition according to claim 109
wherein said (C) is C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride.
111. The composition according to claim 110
wherein said C12-C400 hydrocarbyl substituted
dicarboxylic acid or anhydride is C12-C400 hydrocarbyl
substituted succinic acid or anhydride.
112. The composition according to claim 111
wherein said C12-C400 hydrocarbyl substituted succinic
acid or anhydride is polyisobutenylene succinic acid or
anhydride.
113. The composition according to claim 108
wherein said polyamine (II)(B)(i) comprises ethylene-
polyamine, propylene-polyamine, polyethylenepolyamine or
polypropylenepolyamine.

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114. The composition according to claim 106
wherein said polyamine (II)(B)(i) contains an average of at
least 2 primary amine groups per molecule.
115. The composition according to claim 114
wherein X of (II)(B)(ii) is oxygen.
116. The composition according to claim 115
wherein from about 3 to about 5 equivalents of said amine
based on said primary amine content thereof, are reacted
per mole of said alpha, beta-unsaturated compound
(II)(B)(ii).
117. The composition according to claim 116
wherein said amido amine contains an average of from 1 to 3
amido groups per molecule.
118. The composition according to claim 114
wherein X of (II)(B)(ii) is sulfur.
119. The composition according to claim 118
wherein from about 3 to about 5 equivalents of said
polyamine (II)(B)(i), based on said primary amine content
thereof, are reacted per mole of said alpha, beta-
unsaturated compound (II)(B)(ii).
120. The composition according to claim 119
wherein said thioamido-amine contains an average of from 1
to 3 thioamido groups per molecule.
121. The composition according to claim 108
wherein said polyamine (II)(B)(i) contains at least 2
primary amine groups per molecule.
122. The composition according to claim 121
wherein X of (II)(B)(ii) is oxygen.

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123. The composition according to claim 122
wherein from about 3 to about 5 equivalents of said poly-
amine (II)(B)(i), based on said primary amine content
thereof, are reacted per mole of said alpha,
beta-unsaturated compound (II)(B)(ii).
124. The composition according to claim 123
wherein said amido-amine contains an average of from 1 to 3
amido groups per molecule.
125. The composition according to claim 121
wherein X of (II)(B)(ii) is sulfur.
126. The composition according to claim 64
wherein from about 3 to about 5 equivalents of said poly-
amine (II)(B)(i), based on said primary amine content
thereof, are reacted per mole of said alpha,
beta-unsaturated compound (II)(B)(ii).
127. The composition according to claim 126
wherein said thioamido-amine contains an average of from 1
to 3 thioamido groups per molecule.
128. The composition according to claim 73 wherein
said polyamine (II)(B)(i) contains at least 2 primary amine
groups per molecule.
129. The composition according to claim 128
wherein X of (II)(B)(ii) is oxygen.
130. The composition according to claim 129
wherein from about 3 to about 5 equivalents of said poly-
amine (II)(B)(i) based on said primary amine content
thereof, are reacted per mole of said alpha, beta-
unsaturated compound (II)(B)(ii).

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131. The composition according to claim 130
wherein said amido amine contains an average of from 1 to 3
amido groups per molecule.
132. The composition according to claim 64
wherein X of (II)(B)(ii) is sulfur.
133. The composition according to claim 132
wherein from about 3 to about 5 equivalents of said poly-
amine (II)(B)(i), based on said primary amine content
thereof, are reacted per mole of said alpha, beta-
unsaturated compound (II)(B)(ii).
134. The composition according to claim 133
wherein said thioamido-amine contains an average of from 1
to 3 thioamido groups per molecule.
135. A process for producing composition of
matter useful as multifunctional viscosity improver oil
additive comprising:
(A) providing carboxylic acid material grafted
high molecular weight ethylene copolymer comprising
reaction product of (i) ethylene copolymer having a number
average molecular weight of at least 15,000, and (ii)
monounsaturated carboxylic acid material;
(B) providing amido amine or thioamido amine
compound containing at least one primary amino group
comprising reaction product of (i) at least one polyamine,
and (ii) at least one alpha, beta-unsaturated compound
represented by the formula
<IMG>

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wherein X is sulfur or oxygen, Y is -OR4, -R4, or
<IMG> , and R1, R2, R3, R4 and R5 are
independently selected from hydrogen, hydrocarbyl, and
substituted hydrocarbyl radicals; and
(c) contacting said carboxylic acid material
grafted high molecular weight ethylene copolymer with said
amido amine or thioamido amine in amounts and under
conditions sufficient to effect reaction of at least a
portion of the primary amino group of said amido amine with
at least a portion of said carboxylic acid material groups
in said carboxylic acid material grafted high molecular
weight ethylene copolymer to form said composition of
matter.
136. The process according to claim 135 wherein
in (A) a mixture of (a) carboxylic acid material grafted
high molecular weight ethylene copolymer and (b) C12-
C400 hydrocarbyl substituted dicarboxylic acid or
anhydride or C50-C400 hydrocarbyl substituted mono-
carboxylic acid is provided.
137 The process according to claim 136 wherein
(b) is C12-C400 hydrocarbyl substituted dicarboxylic
acid or anhydride.
138. The process according to claim 137 wherein
said C12-C400 hydrocarbyl substituted dicarboxylic acid
or anhydride is C12-C40 hydrocarbyl substituted
succinic acid or anhydride.
139. The process according to claim 138 wherein
said C12-C400 hydrocarbyl substituted succinic acid or
anhydride is polyisobutylene succinic acid or anhydride.

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140. The process according to claim 135 wherein
said carboxylic acid material grafted high molecular weight
ethylene copolymer is C4-C10 dicarboxylic acid material
grafted high molecular weight ethylene copolymer.
141. The process according to claim 140 wherein
said C4-C10 dicarboxylic acid material grafted high
molecular weight ethylene copolymer is succinic anhydride
grafted high molecular weight ethylene copolymer.
142. The process according to claim 141 wherein
said succinic anhydride grafted high molcular weight
ethylene copolymer is succinic anhydride grafted high
molecular weight ethylene-propylene copolymer.
143. The process according to claim 136 wherein
said carboxylic acid material grafted high molecular weight
ethylene copolymer is C4-C10 dicarboxylic acid material
grafted high molecular weight ethylene copolymer.
144. The process according to claim 143 wherein
said C4-C10 dicarboxylic acid material grafted high
molecular weight ethylene copolymer is succinic anhydride
grafted high molecular weight ethylene copolymer.
145. THe process according to claim 144 wherein
said succinic anhydride grafted high molecular weight
ethylene copolymer is succinic anhydride grafted high
molecular weight ethylene-propylene copolymer.
146. The process according to claim 135 wherein
said carboxylic acid material grafted high molecular weight
ethylene copolymer is C3-C10 monocarboxylic acid
material grafted high molecular weight ethylene copolymer.

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147. The process according to claim 143 wherein
said C4-C10 dicarboxylic acid material grafted high
molecular weight ethylene copolymer is succinic anhydride
grafted high molecular weight ethylene copolymer.
148. The process according to claim 144 wherein
said succinic anhydride grafted high molecular weight
ethylene copolymer is succinic anhydride grafted high
molecular weight ethylene-propylene copolymer.
149. The process according to claim 135 wherein
said carboxylic acid material grafted high molecular weight
ethylene copolymer is C3-C10 monocarboxylic acid
material grafted high molecular weight ethylene copolymer.
150. The process according to claim 146 wherein
said C3-C10 monocarboxylic acid material grafted high
molecular weight ethylene copolymer is C3-C10 mono-
carboxylic acid material grafted high molecular weight
ethylene-propylene copolymer.
151. The process according to claim 136 wherein
said carboxylic acid material grafted high molecular weight
ethylene copolymer is C3-C10 monocarboxylic acid
material grafted high molecular weight ethylene copolymer.
152. The process according to claim 151 wherein
said C3-C10 monocarboxylic acid material grafted high
molecular weight ethylene copolymer is C3-C10 mono-
carboxylic acid material grafted ethylene-propylene
copolymer.
153. The process according to claim 135 wherein
said polyamine (B)(i) comprises polyamines containing from
2 to 60 carbon atoms and from 2 to 12 nitrogen atoms per
molecule.

- 78 -
154. The process according to claim 153 wherein
said polyamine (B)(i) comprises alkylenepolyamine or
polyalkylenepolyamine wherein each alkylene group contains
2 to 6 carbons and alkylenepolyamine or said poly-
alkylenepolyamine contains from 2 to about 5 nitrogen atoms
per molecule.
155. The process according to claim 135 wherein
said carboxylic acid material grafted high molecular weight
ethylene copolymer comprises succinic anhydride grafted
ethylene-propylene copolymer of a number average molecular
weight of at least about 15,000, said polyamine comprises
alkylenepolyamine or polyalkylenepolyamine wherein each
alkylene group contains 2 to 6 carbons and said alkylene-
polyamine or polyalkylenepolyamine contains 2 to about 5
nitrogen atoms per molecule, and X is oxygen.
156. The process according to claim 136 wherein
said polyamine (B)(i) comprises polyamines containing from
2 to 60 carbon atoms and from 2 to 12 nitrogen atoms per
molecule.
157. The process according to claim 156 wherein
said polyamine (B)(i) comprises alkylenepolyamine or
polyalkylenepolyamine wherein each alkylene group contains
2 to 6 carbons and said alkylenepolyamine or poly-
alkylenepolyamine contains from 2 to about 5 nitrogen atoms
per molecule.
158. The process according to claim 136 wherein
said carboxylic acid material grafted high molecular weight
ethylene copolymer comprises succinic anhydride grafted
ethylene-propylene copolymer of a number average molecular
weight of at least about 15,000, and (b) is polyisobutylene

- 79 -
substituted succinic anhydride, said polyamine (B)(i)
comprises alkylenepolyamine or polyalkylenepolyamine
wherein each alkylene group contains 2 to 6 carbons and
said alkylenepolyamine or polyalkylenepolyamine contains 2
to about 5 nitrogen atoms per molecule, and X in (B)(ii) is
oxygen.

Description

- 201~063
FIELD OF THE INVENTION
The invention relates to oil soluble polymeric
compositions of matter useful as multifunctional viscosity
index improver additives, particular viscosity index
improver-dispersant additives, for oleaginous compositions
such as fuel and lubricating oil compositions, and to
oleaginous compositions containing said additives.
BACXG~<OUND OF THE INVENT;~Q~
The concept of derivatizing V.I. improving high
molecular weight ethylene copolymers, with acid moieties
such as maleic anhy~ride, followed by reaction with an
amine to form a V.I.-dispersant oil additive is known as
indicated by the following patents.
U.S. Pat. No. 3,316,177 teaches ethylene-
propylene-diene, which are heated to elevated temperatures
in the pre~.ence of oxygen so as to oxidize the polymer and
cause its reaction with maleic anhydride which is present
during the oxidation. The resulting polymer can then be
reacted with alkylene polyamines.
U.S. Pat. No. 4,089,794 teaches grafting the
ethylene copolymer with maleic anhydride using peroxide in
a lubricating oil solution, wherein the grafting is
pre~erably carried out under nitrogen, followed by reaction
with polyamine.
U.S. Pat. No. 4,137,185 teaches reacting Cl to
C30 monocarboxylic acid anhydrides, and dicarboxylic
anhydrides, such as acetic anhydride, succinic anhydride,
etc. with an ethylene copolymer reacted with maleic
anhydride and a polyalkylene polyamine to inhibit cross
linking and viscosity increase due to further reaction of
any primary amine groups which were initially unreacted.

20~ ~0~3
-- 2 --
U.S. Pat. No. 4,144,181 is similar to 4,137,185 in
that it teaches using a sulfonic acid to inactivate the
remaining primary a~ine qroups when a maleic anhydride
grafted ethylene-propylene copolymer is reacted with a
polyamine.
U.S. Pat. No. 4,169,063 reacts an ethylene
copolymer in the absence of oxygen and chlorine at
temperatures of 150- to 250~C with maleic anhydride
followed by reaction with polyamine.
A number of prior disclosures teach avoiding the
u~e of polyamine having two primary amine groups to thereby
reduce cross-linking problems which become more of a
problem as the number of a~ine moieties added to the
polymer molecule is increased in order to increase
dispersancy .
German Published Application No. P3025274.5
teaches an ethylene copolymer reacted with maleic anhydride
in oil using a long chain alkyl hetero or oxygen-containing
amine.
U.S. Pat. No. 4,132,661 grafts ethylene copolymer,
using peroxide and/or air blowing, with maleic anhydride
and then reacts with a primary-tertiary diamine.
U.S. Pat. No. 4,160,739 teaches an ethylene
copolymer which is grafted, using a free-radical technique,
with alternating maleic anhydride and a second
pol~eri2able monomer such as methacrylic acid, which
material8 ar~ reacted with an amine having a single
primary, or a singl~ secondary, amine group.
U.S. Pat. No. 4,171,273 reacts an ethylene
copolymer with maleic anhydride in the presence of a
free-radical initiator and then with mixtures of C4 to
C~2 n-alcohol and amine s~ch as N-aminopropylmorpholine
or dimethylamino propyl amine to form a V.I.-dispersant
pour depressant additive.
. . ~ . .. - . . ..
. ,, ... , . . ., ,-
,. . : . ,, .. : - , - -

201~0~3
- 3 -
U.s. Pat. No. 4,219,432 teaches maleic anhydride
grafted ethylene copolymer reacted with a mixture o~ an
amine having only one primary group together with a second
amine having two or more primary groups.
German published application No. 2753569.9 shows
an ethylene copolymer reacted with maleic anhydride by a
free-radical technique and then reacted with an amine
having a single primary group.
Ger~an published application No. 2845288 grafts
maleic anhydride on an ethylene-propylene copolymer by
thermal grafting at high temperatures and then reacts with
amine having one primary group.
French published application No. 2423530 teaches
the thermal reaction of an ethylene copolymer with maleic
anhydride at 150-C to 210~C followed by reaction with an
amine having one primary or secondary group.
The early patents such as U.S. Pat. Nos. 3,316,177
and 3,326,804 taught the general concept o~ grafting an
ethylene-propylene copolymer with maleic anhydride and then
reacting with a polyalXylene polyamine such as polyethylene
amines. Subsequently, U.S. Pat. No. 4,089,794 was directed
to using an oil solution for free radical peroxide grafting
the ethylene copolymer with maleic anhydride and then
reacting with the polyamine. This concept had the
advantage that by using oil, the entire reaction could be
carried out in an oil solution to form an oil concentrate,
which i~ the commercial form in which such additives are
~old. This was an advantage over using a volatile solvent
~or tho reactions, which has to be subsequently removed and
r-placed ~y oil to form a concentrate. Subsequently, in
oporating at higher polyamine levels in order to further
incrQase the dispersing effect, increased problems occurred
with the unreacted amine groups cross-linking and thereby
cau~ing visc03ity increase og the oil concentrate during
-, ~ ' ' '
- . .

2~15~3
- 4 -
storage and subsequent formation of haze and i~ some
instancas gelling. Even though one or more moles of the
ethylene polyamine was used per mole of maleic anhydride
during imide formation, cross-linking became more of a
problem as the nitrogen content of the polymers was
increased. One solution was to use the polyamines and then
to react the remaining primary amino groups with an acid
anhydride, preferably acetic anhydride, of U.S. Pat. No.
4,137,185 or the sulfonic acid or U.S. Pat. No. 4,144,181.
The cross-linking problem could also be minimized by
avoidance o~ the ethylene polyamines and instead using
amines having one primary group which would react with the
maleic anhydride while the other amino groups would be
tertiary groups which were substantially unreactive.
Patent~ or published applications showing the use of such
primary tertiary amines noted above are U.S. Pat. No.
4,219,432, wherein a part of the polyamine was replaced
with a primary-tertiary amine; U.S. Pat. No. 4,132,661:
U.S. Pat. No. 4,160,739; U.S. Pat. No. 4,171,273; German
No. P2753569.9; German No. 2,845,288; and French No.
2,423,530.
U.S. Patent No. 4,517,104 discloses polymeric
viscosity index (V.I.~ improver-dispersant additive for
petroleum oils, particularly lubricating oils, comprising a
copolymer o~ ethylene with one or more C3 to C28
alpha-olefins, preferably propylene, which has been gra~ted
wlth acid moieties such as maleic anhydride using a free
radical initiator in a solvent such as lubricating oil, and
then reacted with a carboxylic acid component including
hydrocarbyl substituted succinic anhydride or acid having
12-400 carbon atoms in said hydrocarbyl group or long chain
monocarboxylic acid, and a polyamine having two or more
primary amine groupR. Or the grafted polymer may be
reacted with said acid component prereacted with said
polyamine to for~ salts, amides, imides, etc. and then
.. . . . . .
' '' ' '' ' ' ~ ~ '

2015063
- 5 -
reacted with said grafted olefin polymer. These reactions
can permit the incorporation of varnish inhibition and
dispersancy into ths ethylene copolymer while inhibiting
cross-linking or gelling.
U.S. Patent No. 4,632,769 discloses oil soluble
viscosity index improving ethylene copolymers, such as
copolymers of ethylene and propylene, reacted or grafted
with ethylenically unsaturated carboxylic acid moieties,
preferably maleic anhydride moieties, and then reacted with
polyamines having two or more primary amine groupq and a
C22 to C28 olefin carboxyli~ acid component. These
reactions can permit the incorporation of varnish
inhibition and dispersancy into the ethylene copolymer
while inhibiting cross-linking or gelling.
U.S. Patent 2,921,085 relates to the preparation
of beta-aminopropionamides by reaction of an alkyl amine
with an acrylate to form an alkyl aminopropionate and
reaction of the latter compound with an amine. ~he
re~ulting compounds are disclosed to have utility as
sur~ace active agents, specifically as emulsifying,
wetting, foaming and detergent agents.
U.S. Patent 3,337,609 relates to adducts of
hydroxyalkyl alkylene polyamines and acrylates. The
rosulting adducts are added to polyepoxides to provide
compositions whic~ are suitable for us~ as a barrier
coating for polyethylene surfaces, and for additional end
uses, such as in molding. In addition, the adducts are
disclosed to be useful as catalysts in resin preparation
and as corrosion inhibitors in water systems for ferrous
metals.
U.S. Patent 3,417,149 relates to the preparation
o~ amido-amine compositions, which are useful as epoxy
resin curing agents, by reacting a polyalkylene polyamine
and a fatty amine (comprising a mono- or diamine having as
.
.. ~ .. .

2015~3
- 6 -
one of the substituents on a nitrogen atom a hydrocarbyl
radical having 8 to 24 carbon atoms) with an alpha-beta
unsaturated carbonylic compound. It is disclosed that this
reaction occurs through the Michael addition of an amine
group across the unsaturated group of the carbonylic
compound and through the condensation of an amine group
with the carbonylic group.
U.S. Patent 3,247,163 also relates to curing
agents for polyepoxide compositions, which curing agents
are prepared by rea,,ting an organi,, amine and an acrylate.
U.S. Patent 3,445,441 relates to amino-amido
polymer~ characterized ~y being a reaction product of at
least a polyamine and an acrylate type compound, such as
methyl or ethyl acrylate, and methyl or ethyl
methacrylate. Thff~ patent states that the polymers are
us~e~ul in a wide variety o~ applications, such as
~loculating agents, water clarifying additives, corrosion
inhibitors in oil and gas wells, and as lube oil
additlv,a~4. The patent further discloses that the polymers
may bf,a df,a,rivitized, including acylation with monocarboxylic
acida and polycarboxylic acids, aliphatic dicarboxylic
acld~, aromatic, dicarboxylic acids, for example,
dlglycolic, phthalic, succinic, etc., acids.
U'.S. Patent 3,903,003 relates to lubricating
composltlon~ containing an amido-amine reaction product of
,~ torolnally carboxylated isoprene polymer which is formed
by reacting a terminally carboxylated ~ubstantially
compl,,a~t,,aly hydrogenated polyi~oprene having an average
mol~acular weight between about 20,000 and 250,000 and a
nitrog~,an compound of the group consisting of polyalkylene
amlnes and hydroxyl polyalkylene amines.
U.S. Patent 4,493,771 relates to scale inhibiting
with compounds containing ,,~uaternary ammonium and mathylene
phosphonlc acid groups. Thes,, compounds are derivatives of
f
.

20150~3
-- 7 --
polyamines in which the amine hydrogens have been
substituted with both methylene phosphonic acid groups or
their salts and hydroxypropyl quaternary ammonium halide
groups. The patent discloses that any amine that contains
reactive amino hydrogens can be utilized, for example,
polyglycol amines, amido-amines, oxyacylated amines, and
others.
U.S. Patent 4,459,241 contains a similar
disclosure to U.S. Patent 4,493,771.
The materials of the present invention are an
improvement over those of the aforediscussed prior
disclosures because of their effectiveness and their
ability to provide enhanced lubricating oil dispersancy.
SUMMARY OF THE INVENTION
Compositions of matter useful as multifunctional
viscosity , index improvers for oLea~inous compositions,
including fuel and lubricating oil compositions, comprising
high molecular weight ethylene copolymers, such as
ethylene-~-olefin copolymers, reacted or grafted with
ethylenically unsaturated carboxylic acid materials, such
as maleic anhydride, and reacted with an amido-amine. The
amido-amine is characterized by being a reaction product of
at least one polyamine and an ~ unsaturated compound
of the formula
R2 R3 X
11
Rl _ C = C - C _ Y (I)
wherein X is sulfur or oxygen, Y is -oR4~ -SR4, or
-NR4~R5), and Rl, R2, R3 R4 and R5 are the
same or different and are hydragen or substituted or
unsubstituted hydrocarbyl.

201~063
- 8 -
DETAILED DESCRIPTION OF THE INvENTIoN
The compositions of matter of the instant
invention comprise high molecular weight, i.e., at least
15,000 number average molecular weight, copolymers of
ethylene, preferably copolymers of ethylene and at least
one other C3 to C28 alpha-olefin such as propylene,
reacted or grafted with ethylenically unsaturated
carboxylic acid material to form a grafted ethylene
copolymer, followed by reaction with an amido-amine. These
materials are useful as multifunctional viscosity index
improver additives, particularly viscosity index
improver-dispersant additives for oleaginous compositions
such as fuel and lubricating oil compositions.
ETHYLENE COPOLYMER
Oil soluble ethylene copolymers used in the
invention are those capable of modifying or improving the
viscosity index of oleaginous compositions, particularly
lubricating oil compositions, i.e., polymers useful as V.I.
improvers. ~herefor, they generally will have a number-
average molecular weight (~n) f greater than
about 10,000, preferably at least about 15,000. These
copolymers preferably have number average molecular weights
o~ from about 15,000 to about 500,000, more preferably
about 20,000 to about 300,0C0, and most preferably from
about 30,000 to about 150,000. These V.I. improvers will
generally have a narrow range of molecular weight, as
determined by the ratio of weight-average molecular weight
~) to number-average molecular weight (~n)
Polymers having a ~w/~n of less than 10,
pre~erably less than 7, and more preferably 4 or less are
most desirable. As used herein (~n) and (~w/~n)
are measured by the well known techniques of vapor phase
osmometry (VPO), membrane osmometry and gel permeation
chromatography. In general, polymers having a narrow range
of molecular weight may be obtained by a choice of
~ ' , , , ~ .
. . . - . .
- ' :,- . . .. . .
- ' .'.. ' ~ ' '
..
' - : ':.' ' .' .'. '' ' ,. ' ' .. .''.. ' ' . '

201~0~3
g
synthesis conditions such as choice of principal catalyst
and cocatalyst combination, addition of hydrogen during the
synthesis, etc. Post synthesis treatment such as extrusion
at elevated temperature and under high shear through small
orifices, mastication under elevated temperatures, thermal
degradation, fractional precipitation from solution, etc.
may also be used to o~tain narrow ranges of desired
molecular weights and to break down higher molecular weight
polymer to di~ferent molecular weight grades for V.I. use.
These polymers are prepared from ethylene and
ethylenically unsaturated hydrocarbons including cyclic,
alicyclic and acyclic, containing from 3 to 28 carbons,
e.g. 2 to 18 carbons. These ethylene copolymers may con-
tain from 15 to 9o wt. % ethylene, preferably 30 to 80 wt.
% of ethylene and 10 to 85 wt. ~, preferably 20 to 70 wt.
~ of one or more C3 to C28, preferably C3 to C18
more preferably C3 to C8, unsaturated hydrocarbons,
preferably alpha olefins. While not essential, such
copolymers pre~erably have a degree of crystallinity of
le~5 than 25 wt. %, as determined by X-ray diffraction and
differential scanning calorimetry. Copolymers of ethylene
and propylene are most preferred. Other alpha-olefins
suitable in place of propylene to form the copolymer, or to
be used in combination with ethylene and propylene, to .
~orm a terpolymer, tetrapolymer, etc., l-pentene, l-hexene,
l-heptene, l-octene, l-nonene, l-decene, etc.; also
branched chain alpha-olefins, such as 4-methyl-1-pentene,
4-methyl-1-hexene, 5-methylpentene-1, 4,4-dimethyl-1-
pentene, and 6-methylheptene-1, etc., and mixtures thereof.
The term copolymer as used herein, unless other-
wi9e indicated, includes terpolymers, tetrapolymers, etc.,
of ethylene, said C3-28 alpha-olefin and/or a non-conju-
gated diolefin or mixtures of such diolefins which may also
be used. The amount of the non-conjugated diolefin will
.
.
.. . . .. . .
- .. . - .: . . . . .. .
: .
~ . - : :
. . .

201~063
-- 10 --
generally range from about 0.5 to 20 mole percent, prefer-
ably about 1 to about 7 mole percent, based on the total
amount of ethylene and alpha-olefin present.
Representative examples of non-conjugated d$enes
tha~ may b~ used as the third monomer in the terpolymer
include:
a. Straight chain acyclic dienes such as:
1,4-hexadiene; 1,5-heptadiene; l,~-o~tadiene.
b. Branched chain acyclic dienes such as:
5-methyl-1,4-hexadiene; 3,7-dimethyl 1,60ctadiene;
3,7-dimethyl 1,7-octadiene; and the mixed isomers
o~ dihydro-myrcene and dihydro-cymene.
c. Single ring alicyclic dienes such as:
1,4-cyclohexadiene; 1,5-cyclooctadiene; 1,5-cyclo-
dodecadiene; 4-vinylcyclohexene; 1-allyl-4-
isopropylidene cyclohexane: 3-allyl-cyclopentene;
4-allyl-cyclohexene and 1-isopropenyl-4-(4-
butenyl) cyclohexane.
d. Multi-single ring alicyclic dienes such as:
4,4'-dicyclopentenyl and 4, 4 ' -dicyclohexenyl
diene
e. Multi-ring alicyclic fused and bridged ring
diene~ such as: tetrahydroindene; methyl
tetrahydroindene: dicyclopentadiene; bicyclo
(2.2.1) hepta-2,5-diene; alkyl, alkenyl,
alkylldene, cycloalkenyl and cycloalkylidene
norbornenes such as: ethyl norbornene: 5-methyl-
ene-6-methyl-2-norbornene; 5-methylene-6,6-
dimethyl-2-norbornenet 5-propenyl-2-norbornene;
5-(3-cyclopentenyl)2-norbornene and 5-cyclohexyl-
idene-2-norbornene; norbornadiene; etc.
.'' - . :. .
. - .
- .,. . :, : .
: ,
.

2~ 0~3
.
CARBOXYLIC ACID MATER~A~
The carboxylic acid material which is grafted to
or reacted with the ethylene copolymer to form the grafted
ethylene copolymer is pre~erably ethylenically unsaturated,
preferably monounsaturated, carboxylic acid material and
can be either a monocarboxylic or dicarboxylic acid
material. The dicarboxylic acid materials include (i)
monounsaturated C4 to C10 dicarboxylic acid wherein (a)
the carboxyl groups are vicinyl, i.e., located on adjacent
carbon atoms, and (b) at least one, preferably both, of
~aid adjacent carbon a~oms are part of said
monounsaturation; and (ii) derivatives of (i) such as
anhydride or Cl to C5 alcohol derived mono- or
diesters of (i). Upon reaction with the ethylene copolymer
the monounsaturation of the dicarboxylic acid, anhydride,
or ester becomes saturated. Thus, for example, maleic
anhydride becomes an ethylene copolymer substituted
succinic anhydride.
The monocarboxylic acid materials include ti)
monounsaturated C3 to C10 monocarboxylic acid wherein
th- carbon-carbon bond is conjugated to the carboxy group,
i.e., of the structure
o
11
- C = C - C - ; and
(il) derivatives of (i) such as C1 to C5 alcohol
d-rived monoesters of (i). Upon reaction with the ethylene
copolymer, the monounsaturation of the monounsaturated
carboxylic acid material becomes saturated. Thus, for
xample, acryllc acid becomes an ethylene copolymer
substituted propionic acid, and methacrylic acid becomes an
ethylene copolymer substituted isobutyric acid.
Exemplary of such unsaturated mono- and
dicarboxylic acids, or anhydrides and thereof include
fumaric acid, itaconic acid, maleic acid, maleic anhydride,
chloromaleic anhydride, acrylic acid, methacrylic acid,
. ~ ~,'. .''' - ' . . ~

- 12 -
crotonic acid, cinnamic acid, methyl acrylate, ethyl
acrylate, methyl methacrylate, etc.
Preferred carboxylic acid materials are ~he
dicarboxylic acid anhydrides. Maleic anhydride or a
derivative thereof is particularly preferred as it doe~ not
appear to homopoly~erize appreciably but grafts onto the
ethylene copolymer to give two carboxylic acid
functionalities. Such preferred materials have the generic
formula
R' R "
C - C
= C C = O
o
wherein R' and R'' are independently hydrogen or a halogen.
Additionally, as taught by U.S. Patent Nos.
4,160,739 and 4,161,4~2, various unsaturated comonomers may be
gra~ted on the ethylene copolymer together with the
unsaturated carboxyl~c acid material. Such graft monomer
systems may comprise one or a mixture of comonomers
dir~erent ~rom said unsaturated carboxylic acid material,
and which conta$n only one copolymerizable double bond and
are copolymerizable with said unsaturated acid compo~ent.
Typically, such comonomers do not contain free
carboxylic acid groups and are esters containing alpha-
thyleni¢ unsaturation in the acid or alcohol portion;hydrocarbon~, both aliphatic and aromatic, containing ,
alph~-ethylenic unsaturation, such as the C4-C12 alpha
olerins, ~or example hexene, nonen~, dodecene, etc.;
styrenes, ~or exa~ple styrene, alpha-methyl styrene,
p-methyl styrene, butyl styrene, etc.; and vinyl monomers,
ror example vinyl acetate, vinyl chloride, vinyl ketones
.. , , .~
- . .
'' ' ' ~ '
.
: . . .. :

201~0~'3
- 13 -
such a~ methyl and ethyl vlnyl ketone, and nitrogen
containing vinyl monomer such as vinyl pyridino and vinyl
pyrrolidine, etc. ComonomerS containing functional groups
which may cause crosslinking, gelation or other interfering
reactions should be avoided, although minor amounts of such
comonomers (up to about 10~ ~y weight of the comonomer
system) often can be tolerated.
Specific useful copolymeri2able comonomers include
th~ following:
(A) Esters of saturated acids and unsaturated
alcohols wherein the saturated acids may be monobasic or
polybasic acids containing up to about 40 carbon atoms such
as the following: acetic, propionic, butyric, valeric,
caproic, stearic, oxalic, malonic, succinic, glutaric,
ad~pic, pimelic, suberic, azelaic, sebacic, phthalic,
isophthalic, terephthalic, hemimellitic, trimellitic,
trimesic and the like, including m~xtures. Tho unsaturated
alcohols may be monohydroxy or polyhydroxy alcohols and may
contain up to a~out 40 carbon atoms, such as the
~ollowing: allyl, methallyl, crotyl, l-chloroallyl,
2-chloroallyl, cinnamyl, vinyl, methyl vinyl, l-phenallyl,
butenyl, propargyl, l-cyclohexene-3-ol, oleyl, and the
like, including mixtures.
(B) Esters of unsaturated monocarboxylic acids
containing up to about 12 carbon atoms such as acrylic,
methacrylic and crotonic acid, and an esterifying agent
conta$ning up to about 50 carbon atoms, selected from
~aturated alcohol~ and alcohol epoxides. The saturated
alcohol~ may preferably contain up to about 40 carbon atoms
and include monohydroxy compounds such as: methanol,
ethanol, propanol, ~u~anol, 2-ethylhexanol, octanol,
dod-canol, cyclohexanol, cyclopentanol, neopentyl alcohol,
and benzyl alcohol: and alcohol ethers such as the mono-
mQthyl or monobutyl ethers of ethylene or propylene glycol,
~ ~ . . . . .
:
::
-
- ' ~ . . '' .' : '
, . .
.. - - ~ ..... . .

- 14 -
and the like, including mixtures. The alcohol ep~xides
include fatty alcohol epoxides, glycidol, and various
derivatives of alkylene oxides, epichlorohydrin, and the
like, including mixtures.
The components of the graft copolymerizable system
are used in a ratio of unsaturated carboxylic acid material
monomer component to comonomer component of about 1:4 to
4:1, preferably about 12 to 2:1 by weight.
GR~F~ING OF THE~ E~E COPOLYMER
The grafting of the ethylene copolymer with the
carboxylic acid material may be by any suitable method,
such as thermally by the "ene" reaction, using copolymers
containing unsaturation, such as e~hylene-propylene-diene
polymers either chlorinated or unchlorinated, or more
prererably it is by free-radical induced grarting in sol-
vent, preferably in a mineral lubricating oil as solvent.
The radical grafting is preferably carried out
using ~ree radical initiators such as peroxides, hydro-
peroxides, and azo compounds and preferably those which
have a boiling point greater than about lOO-C. and which
decompose thermally within the grafting temperature range
to provide said free radicals. Representative of these
~re~-radical initiators are a20butyro-nitrile, 2,5-di- -
m~thyl-hex-3-yne-2, 5 bis-tertiary-butyl peroxide (sold.
a~ Lupersol 130) or its hexane analogue, di-tertiary butyl
p-roxide and dicumyl peroxide. The initiator is generally
usod at a level of between about 0.005% and about 1%, based
on the total weight of the polymer solution, and tempera-
tures Or about 150 to 220'C.
The ethylenically unsaturated carboxylic acid
material, such as maleic-anhydride, will be generally used
in an amount ranging from about 0.01% to about 10%,
prererably 0.1 to 2.0%, based on weight of the initial
TM - Trade mark
,- . . ~', . ' ' .
' ~ '
~' . ' ' '

-- 201~01~3
- 15 -
total solution. The aforesaid carboxylic acid material and
free radical initiator are generally used in a weight
percent ratio range of 1.0:1 to ~0:1, preferably 3.0:1 to
6:1.
The initiator grafting is preferably carried out
in an inert atmosphere, such as that obtained by nitrogen
blanketing. While the grafting can b~ carried out in the
presence of air, the yield of the desired graft polymer is
generally thereby decreased as compared ~o grafting under
an inert atmosphere substantially free of oxygen. The
grafting tim~ will usually range from about 0.1 to 12
hoùrs, preferably from about 0.5 to 6 hours, more prefer-
ably 0.5 to 3 hours. The graft reaction will be usually
carried out to at least approximately 4 times, preferably
at least about 6 times the half-life of the free-radical
initiator at the reaction temperature employed, e.g. with
2,5-dimethyl hex-3-yne-2, 5-bis(t-butyl peroxide) 2 hours
at 160-C. and one hour at 170'C., etc.
In the grafting process, usually the copolymer
solution is first heated to grafting temperature and
thereafter said unsaturated carboxylic acid material and
initiator are added with agitation, although they could
have been added prior to heating. When the reaction is
complete, thQ excess acid material can be eliminated by an
inert gas purge, e.g. nitrogen sparging. Preferably the
carboxylic acid material that is added is kept below its
~olubility limit in the polymer solution, e~g. below a~out
1 wt. ~, pre~erably below 0.4 wt. % or less, of free maleic
anhydride based on the total weight of polymer-solvent
solution, e.g. ethylena copolymer mineral lubricatinq oil
solution. Continuous or periodic addition of the
carboxylic acid material along with an appropriate portion
o~ initiator, during the course of the reac~ion, can be
utilized to maintain the carboxylic acid below its

- 201~06~
- 16 -
solubility limits, while still obtaining the desired degree
of total grafting.
In the initiator gra~ting step the maleic
anhydride or other carboxylic acid material used will ~e
grafted onto both the polymer and the solvent for the
reaction. Many solvents such as dichlorobenzene are rela-
tively inert and may be only slightly grafted, while
mineral oil will tend to be more grafted. The exact split
o~ graft between the substrate present depends upon the
polymer and its reactivity, the reactivity and type o~ oil,
the concentration of the polymer in the oil, and also upon
the maintenance o~ the carboxylic acid material in solution
during the course of the reaction and minimizing the
presence o~ dispersed, but undissolved acid, e.g. the
maleic anhydride. The undissolved acid material appears to
have an increased tendency to react to form oil insoluble
materials as opposed to dissolved acid material. ~he split
botween grafted oil and grafted polymer may be measured
empirically from the infrared analyses of the product
dlalyzed into oil and polymer fractions.
The graftin~ is preferably carried out in a
mineral lubricating oil which need not be removed after the
gra~ting step but can be used as the solvent in the
sub~equent reaction of the graft polymer with the amine
material and as a solvent for the end product to form the
lubricating additive concentrate. The oil having attached,
gra~ted carboxyl groups, when reacted with the amine
mat-rial will also be converted to the corresponding
der~vat~ves.
~ he solution grafting step when carried out in the
presence of a high temperature decomposable peroxide can be
accomplished without substantial degradation of the chain
l-ngth (molecular weight) of the ethylene containing
polymer. This can be an advantage as opposed to high

2015063
- 17 -
temperature thermal reactions which depend on degradation
to apparently form free radical reactive sites. Measure-
ment of molecular weights and degradation can be evaluated
by determination of the thickening efficiency (T.E.) of the
polymer as will later be described.
The amount of carboxylic acid material used in the
grafting reaction is an amount which is effective to
provide a grafted ethylene copolymer which upon further
reaction with an amido-amine as described hereinafter
provides a material exhibiting the properties of a
multifunctional viscosity index improver additive, more
specifically a viscosity index improver-dispersant
additive, i.e., a material having both V.I. improving and
dispersancy properties in an oleaginous composition. That
is to say, an amount which is effective to provide, upon
reaction of the grafted ethylene copolymer with the amido
amine, an oleaginous compositicn exhibiting improved
viscometric and dispersancy properties. Generally, this
amount of grafting material, e.g., moles of carboxylic acid
material such as maleic anhydride, is an amount which is
effective to provide a grafted ethylene copolymer, e.g.,
ethylene-alpha-olefin substituted carboxylic acid material
such as ethylene- propylene substituted succinic anhydride,
containing an average number of acid material moieties,
e.g., succinic anhydride, grafted to or present on a 10,000
number average molecular weight segment of a mole of
ethylene copolymer of at least about 0.1, preferably at
least about 0.5, and more preferably at least about 1. The
maximum average number of grafted moieties present per
10,000 average number molecular weight segment of a mole of
ethylene copolymer backbone should not exceed about 10,
preferably about 7 and more preferably about 5.
Preferably, the average number, moles, of grafted moieties
present per mole of ethylene copolymer backbone is at least
about 0.6, preferably at least about 0.8, and more
preferably at least about 1. Preferably, the maximum

201~0~3
- 18 -
average number of grafted moieties grafted to or present
per mole of ethylene copolymer back~one should generally
not exceed about lO, preferably about 7, and more
preferably about 5. Thus, for example, a ~ole of grafted
ethylene copolymer, e.g., ethylene- propylene substituted
succinic anhydride, containing an ethylene copolymer
backbone such as an ethylene- propylene backbone having an
average number molecular weight of 50,000 contains grafted
to said bacXbone an average number of succinic anhydride
moieties of from about 0.5 to about 50, preferably from
about 0.6 to about 10. Typically, from about 0.2 to about
12, preferably from about 0.4 to about 6 moles of said
carboxylic acid material are charged to the reactor per
mole of ethylene copolymer charged.
Normally, not all of the ethylene copolymer reacts
with the carboxylic acid material, e.g., maleic anhydride,
to produce a grafted ethylene copolymer, e.g.,
ethylene-propylene substituted succinic anhydride. The
resultant reaction product mixture, therefore, contains
reacted or grafted ethylene copolymer, e.g.,
ethylene-propylene substituted succinic anhydride,
unreacted or ungrafted ethylene copolymer, and unreacted
grafting material, e.g., maleic anhydride. The unreacted
ethylene copolymer is typically not removed from the
reaction product mixture, and the reaction product mixture,
generally stripped of any unreacted grafting ma~erial, is
utilized as is or is employed for further reaction with the
amine as described hereinafter.
Chaxacterization of the average number of moles of
carboxylic acid material, e.g., maleic anhydride, which
have reacted per mole of ethylene copolymer charged to the
reaction (whether it has undergone reaction or not) is
derined herein as the average number of grafted moieties
grafted to or present per mole of ethylene copolymer

2015063
-- 19 --
backbone. This number is defined solely with reference to
the resulting reaction product mixture. Although the
amount of said unreacted ethylene copolymer contained in
the resulting reaction product mixture can be subsequently
modified, i.e., increased or decreased by techniques known
in the art, such modifications do not alter the average
number of grafted moieties as defined above. The term
grafted ethylene copolymer is intended to refer to the
reaction product mixture whether it has undergone such
modification or not.
AMID0-AMINE
As described above, the amido-amine comprises a
reaction product of at least a polyamine and an alpha, beta
ethylenically unsaturated compound of formula (I) above.
The polyamines useful in this invention comprise
polyamines, most preferably polyalkylene polyamines, of
about 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total
car~on atoms and about 1 to 12, preferably 2 to 12, more
prefcrably 3 to 12, and most preferably at least 5 (e.g., 5
to 9) nitrogen atoms in the molecule. These amines may be
hydrocarbyl amines or may be hydrocarbyl amines including
other groups, e.g, hydroxy groups, alkoxy groups, amide
groups, nitriles, imidazoline groups, and the like. Hydroxy
amines with 1 to 6 hydroxy groups, preferably l to 3
hydroxy groups are particularly useful. Preferred amines
are aliphatlc saturated amines, including those of the
general formulas:
R-N-R~, and R-N-(CH2)s ~ l~(cH2)5 ~ I R
R" R' R " ' R'
(II) (III)
wherein R, R', R "-and R " ' are independently selected from
.
. ' ~
- .

20150~3
- 20 ~
alkylene radicals; and C1 to C12 alkylamino c2 to
C6 alkylene radicals: and wherein R"' can additionally
comprise a moiety o~ the formula:
~ (CH2)9, - N ~ H (IV)
wherein R' is as defined above, and wherein s and s' can be
the same or a different number of from 2 to 6, preferably 2
to 4; and t and t' can be the same or dif ferent and are
numbers of from 0 to 10, preferably 2 to 7, and most
preferably about 3 to 7, with tha proviso that ~he sum of t
and t' is not grea$er than 15. To assure a facile
reaction, it is preferred that R, R', R", R" ', s, s', t
and t' be selected in a manner sufficient to provide the
coDpounds of Formulas II and III with typically at least
one primary or secondary amine group, preferably at least
two primary or secondary amine groups. This can be achieved
by selecting at least one of said R, R', R" or R " ' groups
to be hydrogen or by le~ting t in Formula III be at least
one when R"' i~ H or when the IV moiety possesses a
secondary amino group. The most preferred amine of the
abovo formula~ are represented by Formula III and co~tain
at least two primary amine groups and at least one, and
prQferably at least threQ, secondary amine groups.
Non-llmiting examples o~ suitable amine compounds
lnclude: 1,2-diaminoethane: 1,3-diaminopropane:
1,4-diaminobutane: 1,6-diaminohexane; polye~hylene amines
~uch as diethylene triamine: triethylene tetramine;
t~traethylene pentamine: polypropylene amines such as
1,2-propylene diamine: di-(1,2-propylene)triamine;
d~ 3-propylene) triamine; N,N-dimethyl-1,3-di-
amlnopropanQ: N,N-di-(2-aminoethyl) ethylene diamine;
N,N-d~(2-hydroxyethyl)-1,3-propylen~ diamine;
~-dod-cyloxypropylamine; N-dodecyl-l t 3-propane diamine;
- -. . :

- 21 -
aminopropane; N,N-di-(2-aminoethyl) ethylene diamine;
N,N-di(2-hydroxyethyl)-1,3-propylene diamine;
3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine;
tris hydroxymethylaminomethane (THAM): diisopropanol amine;
diethanol amine; triethanol amine; mono-, di-, and
tri-tallow amines; amino morpholines such as N-(3-amino-
propyl)morpholine; and mixtures thereof.
Other useful amine compounds include: alicyclic
diamines such as 1,4-di(aminomethyl) cyclohexane, and
heterocyclic nitrogen compounds such as imidazolines, and
N-aminoalkyl piperazines o~ the general formula (V):
(CH~ C~2-CH2 ~ C~2~P2-NH ~ H
nl CH2-CH2 n2
. . .
wherein P1 and P2 are the same or different and are
each integers of from 1 to 4, and nl, n2 and n3 are
the same or different and are each integers of from 1 to
3. Non-limiting examples of such amines include
2-pentadecyl imidazoline: N-~2-aminoethyl) piperazine; etc.-
Commercial mixtures of amine compounds mayadvantageously be used. For example, one process for
preparing alkylene amines involv~s the reaction of an alkylene
dihalide (such as ethylene dichloride or propylene dichloride)
with ammonia, which results in a complex mixture of alkylene
amines wherein pairs of nitrogens are joined by alkylene groups,
~orming such compounds as diethylene triamine,
triethylenetetramine, tetraethylene pentamine and isomeric
piperazines. Low cost poly(ethyleneamines) compounds
averaging about 5 to 7 nitrogen atoms per molecule are
available commercially under trade marks such as "Polyamine
H", "Polyamine 400", "Dow Polyamine E-100", etc.
- . - - . : , :
.: . . .. :, ., . :
, . . , : :
.. ..
- ,
-
- . .
. . .
`, . . : ~ ': : ,

- 22 -
NH2 (alkylene O-alkylene ) ~ NH2 (VI)
m
where m has a value of about 3 to 70 and preferably 10 to
35: and
R ( alXylene-~-O-alkylene ) NH2 )
n a (VII)
where "n" has a value of about 1 to 40 with the provision
that the sum o~ all the n's is from about 3 to about 70 and
pre~erably fro~ about 6 to about 35, and R is a polyvalent
saturated hydrocarbon radical of up to ten carbon atoms
whQrein the number of subst~tuents o~ the ~ group is
represented by the value of "a", which is a number of from
3 to 6. The alkylene groups in either form~la (VI) or
(VII) may be straight or branched chains containing about 2
to 7, and preferably about 2 to 4 carbon atoms.
The polyoxyalkylene polyamines of formulas ~VI) or
~VII) above, preferably polyoxyalXylene diamine~ and
polyoxyalkyl~ne tria~inesO may have average molecular
w-ight~ ranging fro~ about 200 to about 4000 and preferably
~rom about 400 to about 2000. The preferred polyoxyal-
kyl~ne polyoxyalkylene polyamines include the
polyoxyethylQne and polyoxypropylene diamines and the .
polyoxypropylene triamines having average molecular weights
ranging from about 200 to 2000. The polyoxyalkylene
polyamines are commercially available and may be obtained,
~or ~xample, from thè Jefferson Chemical Company, Inc.
under the trade marks "Jeffamines D-230, D-400, D-1000, D-2000,
T-403", etc.
Additional amine~ useful in the present invention -
arQ described in U.S. Patent 3,445,441.
Thus, any polyamine, whether aliphatic,
oycloaliphatic, aromatic, heterocylic, etc., can be
- . . . . ~ ~ - .
- - ' " ' ' ' ' ~,: .', , '

-- ` 20~0~3
- 23 -
employed provided it is capable of adding across the
acrylic double bond and amidifying with for example the
carbonyl group (-C[0)-) o~ the acrylate-type compound of
formula I, or with the thiocarbonyl group (-c(S)-) of the
thioacrylate-type compound of formula I.
The alpha, beta ethylenically unsaturated
compounds employed in this invention comprise at least one
member selected from the group consisting of alpha, beta
ethylenically unsaturated compound~ of the formula:
R2 R3 X
11
R - c = C - C ~ Y (I)
wherein X is sulfur or oxygen, Y is -oR4~ -SR4, or
-N~4(R5), and Rl R2 R3, R4 and R5 are the
same or di~ferent and are hydrogen or substituted or
unsubstituted hydrocarbyl.
When Rl~ R2~ R3, R4 or R5 are
hydrocarbyl, these groups can comprise alkyl, cycloalXyl,
aryl, alkaryl, aralkyl or heterocyclic, which can be
substituted with groups which are substantially inert to
any component of the reaction mixture under conditions
selected ~or prepara~ion of the amido-amine. Such
substituent groups include hydroxy, halide te.g., Cl, Fl,
I, Br), -SH and alkylthio. When one or more of Rl
through R5 are alkyl, such alkyl groups can be straight
or branched chain, and will generally contain from 1 to 20,
more usually fro~ 1 to 10, and preferably from 1 to 4,
carbon atoms. Illustrative of such alkyl groups are
methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,
nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and
the like. When one or more of Rl through R5 are aryl,
the aryl group will generally contain from 6 to 10 carbon
atoms (e.g., phenyl, naphthyl).
- ' ' ~ '
.`; : . `

2~1~0~
- 24 -
When one or more of Rl through RS are alkaryl,
the alkaryl group will generally contain from about 7 to 20
carbon atoms, and preferably from 7 to 12 carbon atoms.
Illustrative of such alkaryl groups are tolyl, m-ethyl-
phenyl, o-ethyltolyl, and m-hexyltolyl. When one or more
of R1 through R5 are aralkyl, the aryl component
generally consists of phenyl or (Cl to C6) alkyl-sub-
stituted phenol and the alkyl component generally contains
from 1 to 12 carbon atoms, and preferably from 1 to 6
carbon atoms. Examples of such aralkyl groups are benzyl,
o-ethylbenzyl, and 4-isobutylbenzyl. When one or more of
R1 and R5 are cycloalkyl, the cycloalkyl group will
gonQrally contain from 3 to 12 carbon atoms, and preferably
~rom 3 to 6 carbon atoms. Illustrative of such cycloalkyl
groups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl,
and cyclododecyl. When one or more of R1 through R5
are heterocyclic, the heterocyclic group ~enerally consists
of a compound having at least one ring of 6 to 12 members
in which on or.more ring carbon atoms is replaced by oxygen
or nitro~en. Examples of such heterocyclic groups are
~uryl, pyranyl, pyridyl, piperidyl, dioxanyl, tetrahydro-
furyl, pyrazinyl and 1,4-oxazinyl.
The alpha, beta ethylenically unsaturated
carboxylate compounds employed herein have the following
~ormula:
R2 R3 o
Rl- I = I - C - oR4 (VIII)
wh-rein R , R2, R3, and R4 are the same or
dl~foront and are hydrogen or substituted or unsubstituted
hydrocarbyl as defined above. Examples of such alpha,
b-t~-othylenically unsaturated carboxylate compounds of
~ormula VIII are acrylic acid, methacrylic acid, the
mothyl, ethyl, isopropyl, n-butyl, and isobutyl esters of

- 2~151~
- 2S -
acrylic and methacrylic acids, 2-butenoic acid, 2-hexenoic
acid, 2-decenoic acid, 3-methyl-2-heptenoic acid,
3-methyl-2-butenoic acid, 3-phenyl-2-propenoic acid,
3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid,
2-propyl-2-propenoic acid, 2-isopropyl-2-hexenoic acid,
2,3-dimethyl-2-butenoic acid, 3-cyclohexyl-2-methyl-2-pen-
tenoic acid, 2-propenoic acid, methyl 2-propenoate, methyl
2-methyl 2-propenoate, methyl 2-butenoate, ethyl 2-hex-
enoate, isopropyl 2-decenoate, phenyl 2-pentenoate,
tertiary butyl 2-propenoate, octadecyl 2-propenoate,
dodecyl 2-de~enoate, cyclopropyl 2,3-dimethyl-2-butenoate,
methyl 3-phenyl-2-propenoate, and the like.
The alpha, beta ethylenically unsaturated
carboxylate thioester compounds employed herein have the
following formula:
R2 R3 o
Rl- 1 = 1 ~ C - SR4 ~IX)
wherein R , R2, R3, and R4 are the same or
dl~erent and are hydrogen or substituted or unsubstituted
hydrocarbyl as de~ined above. Examples of such alpha,
beta-ethylenically unsaturated carboxylate thioesters of
~ormula IX are methylmercapto 2-butenoate, ethylmercapto
2-hexenoate, isopropylmercapto 2-decenoate, phenylmercapto
2-pentenoate, tertiary butylmercapto 2-propenoate, octa-
docylmercapto 2-propenoate, dodecylmercapto 2-decenoate,
cyclopropylmercapto 2,3-dimethyl-2-butenoate, methyl-
m-rcapto 3-phenyl-2-propenoate, . methylmercapto 2-pro-
po~oate, methylmercapto 2-methyl-2-propenoate, and the
like.
The alpha, beta ethylenically unsa~urated
carboxyamide compounds employed herein have the following
formula:
R2 R3 0
R~ - C - NR4(R5) (X~
. .

201~0~3
- 26 -
wherein R1, R2, R3, R4 and RS are the same or
different and are hydrogen or substituted or unsubstituted
hydrocarbyl as defined above. Examples of alpha,
beta-ethylenically unsaturated carboxyamides of formula X
are 2-butenamide t 2-hexenamide, 2-decenamide, 3-methyl-
2-heptenamide, 3-methyl-2-butenamide, 3-phenyl-2-propen-
amide, 3-cyclohexyl-2-butenamide, 2-methyl-2-butenamide,
2-propyl-2-propenamide, 2-isopropyl-2-hexenamide, 2,3-di-
methyl-2-butenamide, 3-cyclohexyl-2-methyl-2-pentenamide,
N-methyl 2-butenamide, N,N-diethyl 2-hexenamide, N-iso-
propyl 2-decenamide, N-phenyl 2-pentenamide, N-tertiary
butyl 2-propenamide, N-octadecyl 2-propenamide, N-N-di-
dodecyl 2-decenamide, N-cyclopropyl 2,3-dimethyl-2-buten-
amide, N-methyl 3-phenyl-2-propenamide, 2-propenamide,
2-methyl-2-propenamide, 2-ethyl-2-propenamide and the like.
The alpha, beta ethylenically unsaturated
thiocarboxylate compounds employed herein have the
~ollowing formula:
~2 R3 S
R~ - C - oR4 (XI)
whorein Rl, R2, R3, and R4 are the same or
dlf~erent and are hydrogen or substituted or unsubstituted
hydrocarbyl a~ defined above. Examples of alpha,
beta-ethylenically unsaturated thiocar~oxylate compounds of
~ormula XI are 2-butenthioic acid, 2-hexenthioic acid,
2-decenthioic acid, 3-methyl-2-heptenthioic acid,
3-methyl-2-butenthioic acid, 3-phenyl-2-propenthioic acid,
3-cyclohexyl-2-butenthioic acid, 2-methyl-2-butenthioic
acid, 2-propyl-2-propenthioic acid, 2-isopropyl-2-hex
enthioic acid, 2,3-dimethyl-2-butenthioic acid, 3-cyclo-
hexyl-2-methyl-2-pententhioic acid, 2-propenthioic acid,
methyl 2-propenthioate, methyl 2-methyl 2-propenthioate,
methyl 2-butenthioate, ethyl 2-hexenthioate, isopropyl

201~3
- 27 -
2-decenthioate, phenyl 2-pententhioate, tertiary butyl
2-propenthioate, octadecyl 2-propenthioate, dodecyl
2-decenthioate, cyclopropyl 2,3-dimethyl-2-butenthioate,
methyl 3-phenyl-2-propenthioate, and the like
The alpha, ~eta ethylenically unsaturated dithioic
acid and acid ester compounds employed herein have the
~ollowing formula
R2 R3 S
Rl- 1 = 1 - C - SR4 (XII)
wherein R , R ' R3, and R4 are the same or
dif~erent and are hydrogen or substituted or unsubstituted
hydrocarbyl as defined above Examples of alpha,
bota-ethylenically unsaturated dithioi~ acids and acid
esters of formula XII ara 2-butendithioic acid,
2-hexendithioic acid, 2-decendithioic acid, 3-methyl-2-hep-
tendithioic acid, 3-methyl-2-butendithioic acid,
3-phenyl-2-propendithioic acid, 3-cyclohexyl-2-buten-
dlthioic acid, 2-methyl-2-butendithioic acid,
2-propyl-2-propendithioic acid, 2-isopropyl-2-hexendithioic
acid, 2,3-dimethyl-2-butendithioic acid, 3-cyclo-
hoxyl-2-methyl-2-pentendithioic acid, 2-propendithioic
acid, methyl 2-propendithioate, methyl 2-methyl 2-pro-
ndlthioate, methyl 2-butendithioate, ethyl
2-hexendith~oate, isopropyl 2-decendithioate, phenyl
2-pentendithioate, tertiary butyl 2-propendithioate,
octad-cyl 2-propendithioate, dodecyl 2-decendithioate,
cyclopropyl 2,3-dimethyl-2-butendithioate, methyl
3-phenyl-2-propendithioate, and the like
The alpha, beta ethylenically unsaturated
thiocarboxyamide compounds employed herein have the
following formula
R2 R3 S
R~ I - C - NR4(R5) (XIII)
- -
.
.
.
' . .. . ~ . ' " , ~ '
-: . , . ::

201~063
- 28 -
wherein Rl, R2, R3, R4 and R5 are the same or
different and are hydrogen or substituted or unsubstituted
hydrocarbyl as defined above. Examples of alpha,
beta-ethylenically unsaturated thiocarboxyamides of formula
XIII are 2-butenthioamide, 2-hexenthioamide, 2-decen-
thioamide, 3-methyl-2-heptenthioamide, 3-methyl-2-buten-
thioamide, 3-phenyl-2-propenthioamide, 3-cyclohexyl-2-buten-
thioamide, 2-methyl-2-butenthioamide, 2-propyl-2-propen-
thioamide, 2-isopropyl-2-hexenthioamide, 2,3-di-
methyl-2-butenthioamide, 3-cyclohexyl-2-methyl-2-penten-
thioamide, N-methyl 2-butenthioamide, N,N-diethyl
2-hexenthioamide, N-isopropyl 2-decenthioamide, N-phenyl
2-pententhioamide, N-tertiary butyl 2-propenthioamide,
N-octadecyl 2-propenthioamide, N-N-didodecyl 2-decen-
thioamide, N-cyclopropyl 2,3-dimethyl-2-butenthioamide,
N-methyl 3-phenyl-2-propenthioamide, 2-propenthioamide,
2-methyl-2-propenthioamide, 2-ethyl-2-propenthioamide and
the like.
Preferred compounds for reaction with the
polyamines in accordance with this invention are lower
alkyl esters of acrylic and (lower alkyl) substituted
acrylic acld. Illustrative of such preferred compounds are
compounds o~ the formula:
R3 O
I 11 4
CH2 = C - COR (XIV)
where R3 is hydrogen or a Cl to C4 alkyl group, such
as methyl, and ~4 is hydro~en or a Cl to ~4 alkyl
group, capable of being removed so as to form an amido
group, ~or example, methyl, ethyl, propyl, isopropyl,
butyl, sec-butyl, tert-butyl, aryl, hexyl, etc. In the
prererred embodiments these compounds are acrylic and
methacrylic esters such as methyl, ethyl or propyl
acrylate, methyl, ethyl or propyl methacrylate. When the
selected alpha, beta-unsaturated compound comprises a

2 0 1 ~ ,3
- 29 -
compound of formula I wherein X is oxygen, the resulting
reaction product with the polyamine contains at least one
amido linkage (-C(O)N<) and such materials are herein
termed "amido-amines." Similarly, when the selected alpha,
beta unsaturated compound of formula I comprises a compound
wherein X is sulfur, the resulting reaction product with
the polyamine contains thioamide linkage (-C(S)N<) and
these materials are herein termed "thioamido-amines." For
convenience, the following discussion is directed to the
preparation and use of amido-amines, although it will be
understood that such discussion is also applicable to the
thioamido-amines.
The type of amido-amine formed varies with
reaction conditions. For example, a more linear
amido-amine is formed where substantially equimolar amo~nts
of the unsaturated carboxylate and polyamine are reacted.
~he presence o~ excesse3 of the ethylenically unsaturated
reactant of formula I tends to yield an amido-amine which
is more cross-.linked than that obtained where substantially
equimolar amounts of reactants are employed. Where for
economic or other reasons a cross-linked amido amine using
exce~s amine is desired, generally a molar excess of the
ethylQnically unsaturated reactant of about a~ least 10%,
such as 10-300%, or greater, for example, 25-200%, is
employed. For more efficient cross-linking an excess of
carboxylated mater~al should preferably be used since a
cl~aner reaction ensues. For example, a molar excess of
about 10-100~ or greater such as 10-50%, but preferably an
exces~ of 30-50%, of the carboxylated material. Larger
excess can be employed if desired.
In summary, without considering other factors,
equi~olar amounts of reactants tend to produce a more
linear amido-amina whereas excess of the formula I reactan~
tends to yield a more cross-linked amido-amine. It should
- .. .: : ., . : ,
- .. . . . - ~
- ' . :.
- . ... . . ~ - :
. .
., - , .

201~0~
- 30 -
be noted that the higher the polyamine (i.e., in greater
the number o~ amino groups on the molecule) the greater the
statistical probability of cross-linking since, for
example, a tetraalkylenepentamine, such as tetraethylene
pentamine
H
NH2(CH2CH2N)4H
has more labile hydrogens than ethylene diamine.
These amido-amine adducts so formed are
characterized by both amido and amino groups. In their
simplest embodiments they may be represented by units of
the following idealized formula:
R R R O
l 11
- N ~ A - N ~ CH2 - CH - C -
wherQin the R's, which may be the same or different, are
hydrogen or a substituted group, such as a hydrocarbon
group, ~or example, alkyl, al~enyl, alkynyl, aryl, etc.,
and A is a moiety of the polyamine which, for example, may
b- aryl, cycloalkyl, alkyl, etc., and n is an integer such
a~ 1-10 or greater. The amido-amine adducts preferably
contain an average of form 1 to 3 amido groups per molecule
o~ the amido-amine adduct.
The above ~impli~ied formula represents a linear
amldo-amine polymer. However, crcss-linked polymers may
also be formed by employing certain conditions since the
polymer has labile hydrogens which can further react with
lth-r tha unsaturated moiety by adding across the double
bond or by amidifying with a carboxylate group.
Pre~erably, however, the amido-amines of this
~n~ention are not cross-linked to any substantial degree,
and more preferably are substantially linear.
,: -, -. : . . ,
. .: . . . ~ :
... . . . .
. - ~ .
, . . ' '.. '
.. . . . .
,. .~ . ..
. . .: . , .

201~63
- 31 -
Preferably, the polyamine reactant contains at
least one primary amine (and more preferably from 2 to 4
primary amines) group per molecule, and the polyamine and
the unsaturated reactant o~ formula I are contacted in an
amount of from about l to lO, more preferably from about 2
to 6, and most pre~erably ~rom about 3 to 5, equivalents of
primary amine in the polyamine reactant per mole of the
unsaturated reactant of formula I.
The reaction between the selected polyamine and
acrylate-type compound is carried out at any suitable
temperature. Temperatures up to the decomposition points
of reactants and products can be employed. In practice,
ono generally carries out the reaction by heating the
reactant below lOO-C, such as 80-90'C, for a suitable
per$od of time, such as a few hours. Where an acrylic-type
ester is employed, the progress of the reaction can be
~udged by the removal of the alcohol in forming the amide.
During the early part of the reaction alcohol is removed
quit~ readily below lOO-C in the case of low boiling
alcohols such a~ methanol or ethanol. As the reaction
slows, the temperature is raised to push the polymerization
to completion and the temperature may be raised to 150-C
toward the end of the reaction. Removal of alcohol is a
convenient method of judging the progress and completion of
the reaction which is generally continued until no more
alcohol iB evolved. Based on removal of alcohol, the
yleldR are generally stoichiometric. In more difficult
reactions, yield of at least 95% are generally obtained.
Similarly, it will be understood that the reaction
Or an ethylenically unsaturated carboxylate thioester of
~ormula IX liberates the corresponding HSR4 compound
(e.g., H2S when R4 is hydrogen) as a ~y-product, and
the react$on o~ an ethylenically unsaturated carboxyamide
of formula X liberate~ the corresponding HNR4(R5~
.. .
,: -: , ' .
. .

201~063
- 32 -
compound (e-g-, ammonia when R4 and R5 are each
hydrogen) as by-product.
The reaction time involved can vary widely
depending on a wide variety of factors. For example, there
is a relationship between time and temperature. In
general, lower temperature demands longer times. Usually,
reaction times of from about 2 to 30 hours, such as 5 to 25
hours, and preferably 3 to 10 hours will be employed.
Although one can employ a solvent, the reaction
can be run without the use of any solvent. In fact, where
a high degree of cross-linking is desired, it is preferably
to avoid the use of a solvent and most particularly to
avoid a polar solvent such as water. However, taking into
consideration the effect of solvent on the reaction, where
desired, any suitable solvent can be employed, whether
organic or inorganic, polar or non-polar.
As an example of the amido-amine adducts, the
reaction of tetraethylene pentaamine (TEPA) with methyl
acrylate can be illustrated as follows:
O
H2NtCH2CH2NH]3CH2CH2NH2 + CH2=CH C-OCH3
O ~
H2N~cH2cH2NH~3cH2cH2NHc~2cH2cN~cH2cH2[NHcH2cH2]3 2
REACTION OF GRAFTED ETHYLENE
COPOLYMER WITH AMIDO AMINE
The grafted high molecular weight ethylene
copolymer, preferably in solution, such as an oil solution,
containing 5 to 95 wt.%, preferably 5 to 30 wt. %, and more
preferably 10 to 20 wt.% of said grafted ethylene
copolymer, is readily reacted with the amido-amine by
introducing the amido amine into said grafted ethylene
copolymer containing solution and heating at a temperature
.
. , . : -

2015~63
- 33 -
of from about 100C to 250~C, preferably from 125 to 175'C,
for from about 1 to lO hours, usually about 2 to about 6
hours. The heating is preferably carried out, in the case
of ethylene copolymer substituted dicarboxylic acid
material, to favor formation of imides or mixtures of
imides and amides rather than amides and salts. In the
case of ethylene copolymer substituted monocarboxylic acid
material heating is preferably carried out to favor
formation of amides rather than salts. Removal of water
assures completion of the imidation/ amidation reaction.
Reaction ratios can vary considerably, depending upon the
reactants, amounts of excess, type of bonds formed, etc.
Generally, from about 1 to 5, preferably from about 1.5 to
3 moles of ethylene copolymer substituted monocarboxylic or
dicarboxylic acid moiety content, e.g., grafted succinic
anhydride content, is used per equivalent of amido amine
reactant, e.g., amine.
An example of the reaction of an amido amine
reactant with ethylene copolymer substituted dicarboxylic
acid material is the reaction of ethylene-propylene
copolymer substituted succinic anhydride (EPSA) with a poly
amido-amine having two terminal -NH2 groups, which can be
illustrated as follows:
EP r
O + H2N t (CH2)3 NHC (CH2)3NH ~ t (CH2)3 NHC~CH2)3 ~ NH2
O
r 1 r
N t (CH2)2 NHC(CH2~3N~ ~ (CH2)2 NHC(CH2~3 ~ NH2
,
-- .

20150~3
- 34 -
wherein x and y are each integers of from 0 to 10, with the
proviso that the sum of x + y is at least 1, e.g., 1 to 20.
An example of the reaction of an amido-amine
reactant with an ethylene copolymer substituted monocar-
boxylic acid material is the reaction of ethylene-propylene
copolymer substituted propionic acid (EPA) with a poly
amido-amine having two terminal -N~2 groups, which can be
illustrated as follows:
O o
EP - CH2C-O~ + H2N(CH2~2NH _ zl x-22 y~C(CH2~2NH(CH2)2NH
0 ~ o H O
.. I .. I -
EP -CH2C-O----N(CH2)2NH-ZlX-Z2y~ C(CH2)2NH(CH2)2N-O-C-CH2-EP
wherein x and y are each integers of from 0 to 10, with the
proviso that the sum of x + y is at least 1, e.g., 1 to 20
and wherein 21 and z2 are the same or different and are
each moieties of the formula:
o
- C(CH2) 2NH(CH2) 2NH
~ t will be understood that the amido-amine reac~-
ant can be employed alone or in admixture with any of the
above described amines, such as the polyalkylene poly-
amines, useful in preparing the amido-amine reactant.
Prefera~ly, the ethylene copolymer substituted
mono- or dicarboxylic acid material and amido-amine will be
contacted for a time and under conditions sufficient to
react substantially all o~- the primary nitrogens in the
amido-amine reactant. The progress of this reaction can be
~ollowed by infra-red analysis.
.
- . . . .
.. .
.. : : : . - . :
- --. . .- - . . :
. :. - , :; ' '.' . . ~ . , - - , . .

201~063
- 35 -
This reaction can be conducted in a polar or
non-polar solvent, e.g., xylene, toluene, benzene, and the
like, and is preferably conducted in the presence of a
mineral or synthetic lubricating oil.
In another, and generally preferred, embodiment of
the instant invention, the grafted high molecular weight
ethylene copolymer is reacted with the amido-amine and a
carboxylic acid component or with the preformed reaction
products, e.g., salts, amides, imides, of said amido-amine
and carboxylic acid component.
CARBOXYLIC_ACID COMPONENT
The carboxylic acid component includes:
hydrocarbyl substituted dicarboxylic acid or anhydride,
preferably succinic anhydride or acid, having 12 to 49
carbons, preferably 16 to 49 carbons in said hydrocarbyl
group; long chain monocarboxylic acid of the formula RCOOH
where R is a hydrocarbyl group of about 50 to about 400
carbons: and long chain hydrocarbyl substituted
dicarboxylic acid or anhydride, preferably succinic
anhydride or acid, having from about 50 to about 400
carbons in said hydrocarbyl group. The preferred
carboxylic acid component is the long chain hydrocarbyl
substituted dicarboxylic acid or anhydride, preferably
succinic acid or anhydride, having from about 50 to about
400 carbon atoms in said hydrocarbyl group. Said
hydrocarbyl groups are essentially aliphatic and include
alkenyl and alkyl groups. The longer chain acids and
anhydrides are preferred, particularly when the grafting
reaction is carried out in lubricating oil.
The about C50-C400 hydrocarbyl subtituted
dicarboxylic acid or anhydride includes the reaction
product of the C50-C400 hydrocarbon polymer, generally
a polyolefin, with (i) monounsaturated C4 to C10
dicarboxylic acid wherein (a) the carboxyl groups are
vicinyl, i.e., located on adjacent carbon atoms, and (b) at
lea~t one, preferably both, of said adjacent carbon atoms
.
.
.

20~0~
- 36 -
are part of said monounsaturation; or with (ii) derivatives
of (i) such as anhydrides of (i). Upon reaction with the
hydrocarbon polymer, the monounsaturation of the
dicarboxylic acid, anhydride, etc. becomes saturated. Thus
for example, maleic anhydride becomes a hydrocarbyl
substituted succinic anhydride.
Typically, from about 0.7 to about 4.0 (e.g., 0.8
to 2.6), preferably from about 1.0 to about 2.0, and most
preferably from about 1.1 to about 1.7 moles of said
unsaturated ~4 to C10 dicarboxylic acid, anhydride or
ester are charged to the reactor per mole of polyolefin
charged.
Normally, not all of the polyolefin reacts with
the unsaturated acid or derivative and the hydrocarbyl
substituted dicarboxylic acid material will contain
unreacted polyolefin. The unreacted polyolefin is
typically not removed from the reaction mixture (because
such removal is difficult and would be commercially
infeasible) and the product mixture, stripped of any
unreacted monounsaturated C4 to C10 dicarboxylic acid
or anhydridej is employed as the carboxylic acid component.
Characterization of the average number of moles of
dicarboxylic acid or anhydride, which have reacted per mole
of polyolefin charged to the reaction (whether it has
undergone reaction or not) is defined herein as
functionality. Said functionality is based upon (i)
determination of the saponification number of the r sulting
product mixture using potassium hydroxide; and (ii) the
number average molecular weight of the polymer charged,
using techni~ues well known in the art. Functionality is
defined solely with reference to the resulting product
mixture~ Although the amount of said reacted polyolefin
contained in the resulting product mixture can be
subsequently modified, i.e., increased or decreased by
techniques known in the art, such modifications do not

-- ~ 20150G3
- 37 -
alter functionality as defined above. The term
C50-C400 hydrocarbyl substituted dicarboxylic acid
material is intended to refer to the product mixture
whether it has undergone such modification or not.
Accordingly, the functionality of the C50-c400
hydrocarbyl substituted dicarboxylic acid material will be
typically at least about 0.5, preferably at least about
0.8, and most preferably at least about 0.9 and will vary
typically from about 0.5 to about 2.8 (e.g., 0.6 to 2),
preferably from about 0.8 to about 1.4, and most preferably
from about 0.9 to about 1.3.
Exemplary of such unsaturated dicarboxylic acids
or anhydrides thereof are fumaric acid, itaconic acid,
maleic acid, maleic anhydride, chloromaleic acid,
chloromaleic anhydride, etc.
Preferred about C50 to about C400 olefin
polymers for reaction with the unsaturated dicarboxylic
acids or derivatives thereof are polymers comprising a
ma~or molar amount f C2 ~ C10, e-g-, C2 to C5
monoolefin. Such olefins include ethylene, propylene,
butylene, isobutylene, pentene, octene-1, styrene, etc.
The polymers can be homopolymers such as polyisobutylene,
a~ well as copolymers of two or more of such olefins suoh
as copolymers of: ethylene and propylene; butylene and
isobutylene; propylene and isobutylene; etc. Other
copolymers include those in which a minor molar amount of
the copolymer monomers, e.g., 1 to 10 mole %, is a C4 to
C18 non-conjugated diolefin, e.g., a copolymer of
isobutylene and butadiene; or a copolymer of ethylene,
propylene and 1,4-hexadiene; etc.
In some cases, the olefin polymer may be
completely saturated, for example an ethylene-propylene
copolymer made by a Ziegler-Natta synthesis usig hydrogen
as a moderator to control molecular weight.
The olefin polymers used will usually have number
average molecular weights within the range of about 700 and

2015063
- 38 -
about 5,600, more usually between about 800 and about
3000~ Particularly useful olefin polymers have number
average molecular w~ights within the range of about 900 and
about 2500 with approximately one terminal double bond per
polymer chain. An especially useful starting material is
polyisobutylene. The number average molecular weight for
such polymers can be determined by several known
techniques. A convenient method for such determination is
by gel permeation chromatography (GPC) which additionally
provides molecular weight distribution information, see w.
W. Yau, J. J. Kirkland and D> D. Bly, ~Modern Size
Exclusion Liquid Chromatography", John WIley and Sons, New
York, 1979.
Processes for reacting the about CSO to about
C400 olefin polymer with the C4_10 unsaturated
dicarboxylic acid or anhydride are known in the art. For
example, the olefin polymer and the dicarboxylic acid or
derivative may be simply heated together as disclosed in
U.S. Patents 3,361,673 and 3,401,118 to cause a thermal
"ene" reaction to take place. Or, the olefin polymer can
be first halogenated, for example, chlorinated or
brominated to about 1 to ~ wt. %, preferably 3 to 7 wt. %
chlorine, or bromine, based on the weight of polymer, by
passin~ the chlorine or bromine through the polyolefin at a
temperature of 60 to 250C, e.g. 120 to 160CC, for about
0.5 to 10, preferably 1 to 7 hours. The halogenated
polymer may then be reacted with sufficient unsaturated
acid or derivative at 100 to 250~C, usually about 180 to
235'C, for about 0.5 to 10, e.g. 3 to 8 hours, so the
product obtained will contain the desired number of moles
of the unsaturated acid or derivative per mole of the
halogenated polymer. Processes of this general type are
taught in U.S. Patents 3,087,936; 3,172,892; 3,272,746 and
others.
Alternatively, the olefin polymer, and the
unsaturated acid or derivative are mixed and heated while
- : ,
~ : . . .

-- 39 --
f
adding chlorine to the hot material. Processes of this
type are disclosed in U.S. Patents 3,215,707; 3,231,587;
3,912,764; 4,110,349; and in U.K. 1,550,219.
By the use of halogen, about 65 to 95 wt. % of the
polyolefin, e.g. polyisobutylene wili normally reacted with
the dicarboxylic acid or derivative. Upon carrying out a
thermal reaction without the use of halogen or a catalyst,
then usually only about 50 to 75 wt. % of the polyiso-
butylene will react. Chlorination helps increased the
reactivity.
Particularly pre~erred as the acid component is
polyisobutenyl succinic anhydride.
PRE-REACTED AMIDO AMINE-CARBOXYLIC ACID COMPONENT
The aforesaid amido-amine and carboxylic acid
component may be pre-reacted, with the acid being generally
attached to the amido-amine through salt, imide, amide, or
other linkages so that a primary or secondary amine group
o~ the amido-amine is s~ill available for reaction with the
acid moieties of the grafted high molecular weight ethylene
copolymer. A convenient source of these pre-reacted
materials are the lubricating oil dispersant, provided they
retain primary amine groups capable of further reaction ~-
with the grafted ethylene copolymer, described in U.S. Patent
No. 4,857,217 issued August 15, 1989 and Canadian Appl~cation
Serial No. 2,001,460 filed October 25, 1989.
The grafted high molecular weight ~thylene
copolymer i5 reacted with the amido-amine and carboxylic
acid component or pre-reacted amido-amine-carboxylic acid
component substantially as described hereinafore for the
reaction of the grafted high molecular weight ethylene
copolymer with the amido-amine. Thus, for example a
reaction mixture containing the grafted high molecular
weight ethylene copolymer, e.g., ethylene-propylene
- . , ' ~ .
I' " ~ '

- 201~
- 40 -
substituted succinic anhydride, and carboxylic acid
component, e.g., polyisobutylene substituted succinic
anhydride, is prepared by admixing these two reactants, and
the amido-amine is then introduced into this reaction
mixture and the reaction is carried out as described
hereinafore. Alternatively, the carboxylic acid component
and amido-amine may be added substantially simultaneously
to a reaction mixture containing the grafted high molecular
weight ethylene copolymer.
Generally, the amount of the carboxylic acid
component utilized is an amount sufficient to provide about
0.5 to about 4, preferably from about 1 to about 2 moles of
said carboxylic acid component per molar amount of the
carboxylic acid moieties present in the grafted ethylene
copolymer. For example, with a grafted ethylene-propylene
copolymer of about 40,000 ~n~ i.e., a thickening
efficiency of about 2.1 g and averaging 4 succinic
anhydride groups per molecule, about 4 moles of
polyisobutenyl succinic anhydride would preferably be used
per mole of grafted copolymer. Generally, from about 1 to
5, preferably from about 1.5 to 3 moles of the combined
carboxylic acid moiety content of the grafted ethylene
copolymer and the carboxylic acid content are used per
equivalent of amido-amine reactant, e.g., amine.
The compositions of matter of the instant
invention, i.e., grafted ethylene copolymers reacted with
the amido-amine, can be post-treated with a variety of
material~, particularly acid materials! to inactivate any
remaining primary amino groups of the adduct and thereby
prevent crosslinking and gellation of the adduct. Thus,
for example, the adduct may be post-reacted or post-treated
with Cl ~ C30 monocarboxylic acids or anhydrides,
preferably acetic anhydride, or unsubstituted or C1 -
C30 monocarboxylic monocarboxylic acids or anhydrides,preferably acetic anhydride, or unsubstituted or Cl to
C28 hydrocarbyl substituted dicarboxylic acid anhydrides
-
: - :
: .
-', ' ~ .' ' ' ' . ~ '

- 41 -
as disclosed in U.S. Patent No. 4,137,185, incorporated
herein by reference; and the sulfonic acids of U.S. Patent
No. 4,144,181.
The multifunctional VlSCOslty index improvers of
this invention can be used alone or in admixture with other
viscosity index improvers ox dispersants. The other
viscosity index improvers or viscosity modifiers are
generally high molecular weight hydrocarbon polymers
including polyesters. These other viscosity modifiers may
also be derivatized, as by grafting with a carboxylic acid
material of the type described hereinafore and thereafter
reacting with a polyamine of the type described hereinafore
as a polyol, to include other properties or functions, such
as the addition of dispersancy properties. These oil
soluble viscosity modifying polymers will generally have
number average molecular weights of from 103 to 106,
preferably 104 to 1o6, e.g., 20,000 to ~50,000, as
determined by gel permeation chromatography or osmometry.
Examples of suitable hydrocarbon polymers include
homopolymers and copolymers of two or more monomers of C2
to C30, e.g. C2 to C8 olefins, including both alpha
olefins and internal olefins, which may be straight or
branched, aliphatic, aromatic, alkyl-aromatic,
cycloaliphatic, etc. Frequently they will be of ethylene
with C3 to C30 olefins, particularly preferred being
the copolymers of ethylene and propylene. Other polymers
can be used such as polyisobutylenes, homopolymers and
copolymers of C6 and higher alpha olefins, atactic
polypropylene, hydrogenated polymers and copolymers and
terpolymers of styrene, e.g. with isoprene andJor butadiene
and hydrogenated derivatives thereof. ~he polymer may be
degraded in molecular weight, for example by mastication,
- ; , . : .
,:
'

201.~6~3
- 42 -
extrusion, oxidation or thermal degradation, and it may be
oxidized and contain oxygen. Also included are derivatiZed
polymers such as post-grafted interpolymers of
ethylene-propylene with an active monomer such as maleic
anhydride which may be further reacted with an alcohol, or
amine, e.g. an alkylene polyamine or hydroxy amine, e.g.
see U.S. Patent Nos. 4,089,794; 4,160,739; 4,137,185; or
copolymers of ethylene and propylene reacted or grafted
with nitrogen compounds such as shown in U.S. Patent Nos.
4,068,056; 4,068,058; 4,146,489 and 4,149,984.
The preferred hydrocarbon polymers are ethylene
copolymers containing from 15 to 90 wt.% ethylene,
preferably 30 to 80 wt.% of ethylene and 10 to 85 wt.%,
preferably 20 to 70 wt.% of one or more C3 to C28,
preferably c3 to C18, more preferably C3 to C8,
alpha-olefins. While not essential, such copolymers
preferably have a degree of crystallinity of less than 25
wt.~, as determined by X-ray and differential scanning
calorimetry. Copolymers of ethylene and propylene are most
preferred. Other alpha-olefins suitable in place of
propylene to form the copolymer, or to be used in combin-
ation with ethylene and propylene, to form a terpolymer,
tetrapolymer, etc. , include l-butene, 1-pentene, l-hexene,
1-heptene, l-octene, 1-nonene, l-decene, etc.; also
bra~ched chain alpha-olefins, such as 4-methyl-1-pentene,
4-methyl-1-hexene, 5-methylpentene-1, 4,4-dimethyl-1-
pentene, and 6-methylheptene-1, etc., and mixtures thereof.
Terpolymers, tetrapolymers, etc., of ethylene,
said C3_28 alpha-olefin, and a non-conjugated diolefin or
mlxtures of such diolefins may also be used. The amount of
the non-conjugated diolefin generally ranges from about 0.5
to 20 mole percent, preferably from about 1 to about 7 mole
percent, based on the total amount of ethylene and
alpha-olefin present.
The polyester V.I. improvers are generally
polymers of esters of ethylenically unsaturated C3 to
.
- - ~
- : .
- . - .

- 20150~
- 43 -
C8 mono- and dicarboxylic acids such as methacrylic and
acrylic acids, maleic acid, maleic anhydride, fumaric acid,
etc.
Examples of unsaturated esters that may be used
include those of aliphatic saturated mono alcohols of at
least 1 carbon atom and preferably of from 12 to 20 carbon
atoms, such as decyl acrylate, lauryl acrylate, stearyl
acrylate, eicosanyl acrylate, docosanyl acrylate, decyl
methacrylate, diamyl fumarate, lauryl methacrylate, cetyl
methacrylate, stearyl methacrylate, and the like and
mixtures thereof.
Other esters include the vinyl alcohol esters of
C2 to C22 fatty or mono carboxylic acids, preferably
saturated such as vinyl acetate, vinyl laurate, vinyl
palmitate, vinyl stearate, vinyl oleate, and the like and
mixtures thereof. Copolymers of vinyl alcohol esters with
unsaturated acid esters such as the copolymer of vinyl
acetate with dialkyl fumarates, can also be used.
The esters may be copolymerized with still other
unsaturated monomers such as olefins, e.g. 0.2 to 5 moles
f C2 ~ C20 aliphatic or aromatic olefin per mole of
unsaturated ester, or per mole of unsaturated acid or
anhydride followed by esterification. For example,
copolymers of styrene with maleic anhydride esterified with
alcohols and amines are known, e.g., see U.S. Patent
3,702,300.
Such ester polymers may be grafted with, or the
ester copolymerized with, polymerizable unsaturated
nitrogen-containing monomers to impart dispersancy to the
V.I. improvers. Examples of suitable unsaturated
nitrogen-containing monomers include those containing 4 to
carbon atoms such as amino substituted olefins as
p-(beta-diethylaminoethyl)styrene; basic nitrogen-con-
taining heterocycles carrying a polymerizable ethylenically
unsaturated substituent, e.g. the vinyl pyridines and the
vinyl alkyl pyridines such as 2-vinyl-5-ethyl pyridine,

~V150~3
, . ,
2-methyl-5-vinyl pyridine, 2-vinyl-pyridine, 4-vinyl-
pyridine, 3-vinyl-pyridine, 3-methyl-5-vinyl-pyridine,
4-methyl-2-vinyl-pyridine, 4-ethyl-2-vinyl-pyridine and
2-butyl-1-s-~inyl-pyridine and the like.
N-vinyl lactams are also suitable, e.g. N-vinyl
pyrrolidones or N-vinyl piperidones.
The vinyl pyrrolidones are preferred and are
exemplified by N-vinyl pyrrolidone, N-(l-methylvinyl)
pyrrolidone, N-vinyl-5-methyl pyrrolidone, N-vinyl-3,
3-dimethylpyrrolidone, N-vinyl-5-ethyl pyrrolidone, etc.
Dispersants maintain oil insolubles, resulting
from oxidation during use, in suspension in the fluid thus
preventing sludge flocculation and precipitation as
deposition on metal parts. Suitable dispersants include
alkyl succinimides, the reaction product of oil-soluble
polyisobutylene succinic anhydride with polyamines such as
tetraethylene pentamine, and borated salts thereof. Such
dispersants are disclosed, inter alia, in Belgium Patent
No. 658,236 and U.S. Patent No. 3,272,746.
Other dispersants include the esters derived from
long chain hydrocarbon substituted dicarboxylic acid
material and hydroxy compounds such as monohydric and
polyhydric alcohols or aromatic compounds such as phenols
and naphthols, etc. The polyhydric alcohols are the most
preferred hydroxy compound and preferably contain from 2 to
about 10 hydroxy radicals, for example, ethylene glycol,
diethylene qlycol, triethylene glycol, tetraethylene
glycol, dipropylene glycol, and other alkylene glycols in
which the alkylene radical contains from 2 to about 8
carbon atoms. Other useful polyhydric alcohols include
glycerol, mono-oleate of glycerol, monostearate of
glycerol, monomethyl ether of glycerol, pentaerythritol,
dipentaerythritol, and mixtures thereof.
The ester dispersant may also be derived from
unsaturated alcohols such as allyl alcohol, cinnamyl
alcohol, propargyl alcohol, 1-cyclohexane-3-ol, and oleyl
~: . . . : .
. .. .
. : : . . ,
: . . - ~ :.
- , : ~ - . . :
- : ,

201~06~
- 45 --
alcohol. Still other classes of the alcohols capable of
yielding the esters of this invention comprise the
ether-alcohols and amino-alcohols including, for example,
the oxy-alkylene, oxy-arylene-, amino-alkylene-, and
amino-arylene-substituted alcohols having one or more
oxy-alkylene, amino-alXylene or amino-arylene oxy-arylene
radicals. They are exemplified by Cellosolve, Carbitol,
N,N,N',N'-tetrahydroxy-trimethylene di-amine, and
ether-alcohols having up to about 150 oxy-alkylene radicals
in which the alkylene radical contains from 1 to about 8
carbon atoms.
The ester dispersant may be di-esters of
dicarboxylic acids (e.g., succinic acid or anhydride) or
acidic esters, i.e., partially esterified succinic acids;
as well as partially esterified polyhydric alcohols or
phenols, i.e., esters having free alcohols or phenolic
hydroxyl radicals. Mixtures of the above illustrated
esters likewise are contemplated within the scope of this
invention.
The ester dispersant may be prepared by one of
several known methods as illustrated for example in U.S.
Patent 3,3~1,022. The ester dispersants may also be
borated, similar to the nitrogen containing dispersants.
Hydroxyamines which can be reacted with the
polymer-substituted monocarboxylic acid materials to form
dispersants include 2-amino-1-butanol, 2-amino-2-methyl-
l-propanol, p-(beta-hydroxyethyl)-aniline, 2-amino-1-
propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,
3-propane-diol, 2-amino-2-ethyl-1, 3-propanediol,
N-(beta-hydroxy-propyl)-N'-(beta-aminoethyl~-piperazine,
tris(hydroxymethyl) amino-methane (also known as
trismethylolaminomethane), 2-amino-1-butanol, ethanolamine,
beta-(beta-hydroxyethoxy)ethylamine, and the like.
Mixtures of these or similar amines can also be employed.
'rhe above description of nucleophilic reactants suitable
for reaction with the polymer-substituted monocarboxylic

~ 2~1~0~3
- 46 -
acid materials includes amines, alcohols, and compounds of
mixed amine and hydroxy containing reactive functional
groups, i.e., amino-alcohols.
The tris(hydroxymethyl) amino methane (THAM) can
be reacted with the aforesaid acid materials to form
amides, imides or ester type additives as taught by U.K.
984,409, or to form oxazoline compounds and borated
oxazoline compounds as described, for example, in U.S.
4,102,798; 4,116,876 and 4,113,639.
The multifunctional viscosity index improvers of
the present invention can be incorporated into a
lubricating oil in any convenient way. Thus, they can be
added directly to the oil by dispersing or dissolving the
same in the oil at the desired level of concentration of
the multifunctional viscosity index improvers. Such
blending into the additional lube oil can occur at room
temperature or elevated temperatures. Alternatively, the
multifunctional viscosity index improvers can be blended
with a suitable oil-soluble solvent and base oil to form a
concentrate, and then blending the concentrate with a
lubricating oil basestock to obtain the final formulation.
Such multifunctional viscosity index improver concentrates
will typically contain (on an active ingredient (A.I.)
basis) from about 3 to about 45 wt.%, and preferably from
about 10 to about 35 wt.%, multifunctional viscosity index
improver additive, and typically from about 30 to 90 wt.~,
preferably from about 40 to 60 wt.~, base oil, based on the
concentrate weight.
The lubricating oil basestock for the
multifunctional viscosity index improver typically is
adapted to perfo~m a selected function by the incorporation
of additional additives therein to form lubricating oil
compositions (i.e., formulations).
The amounts of the multifunctional viscosity
improver additives of the instant invention which are
incorporated into an oleaginous composition, e.g.,
.
: . ' .'' ` ' ,. . ~ . ~ ' '
.
,.

- 201~6~
- 47 -
lubricating oil, is an amount which is effective to improve
the viscometric properties, e.g., viscosity index, of said
oleaginous composition and impart dispersancy thereto,
i.e., a viscosity improving and dispersant effective
amount. Generally, this amount is from about 0.01 to about
20, preferably from about 0.1 to about 10, and more
preferably from about 0.2 to about 5 weight percent, based
on the wei~ht of the oleaginous composition.
The oleaginous composition into which the
multifunctional viscosity improvers or modifiers of the
instant invention are incorporated or added include
lubricating oil compositions, e.g., automatic transmission
fluids, heavy duty oils suitable for gasoline and diesel
engines, etc.
The multifunctional viscosity improvers of this
invention may be added to the oleaginous composition in the
form of an oil concentrate. Typically such oil concentrate
contains from about 5 wt.% up to about 49 wt.%, preferably
7 to 25 wt.%, of the multifunctional viscosity improver in
oil, e.g., mineral lubricating oil.
The fully formulated oil compositions, or the oil
concentrate, may optionally contain other conventional
additives such as pour point depressants, antiwear agents,
antioxidants, other viscosity index improvers, dispersants,
corrosion inhibitors, anti-foaming agents, detergents, rust
inhibitors, friction modifiers, and the like.
Corrosion inhibitors, also known as anti-corrosive
agents, reduce the degradation of the metallic parts
contacted by the lubricating oil co~position. Illustrative
of corrosion inhibitors are phosphosulfurized hydrocarbons
and the products obtained by reaction of a
phosphosulfurized hydrocarbon with an alkaline earth metal
oxide or hydroxide, preferably in the presence of an
alkylated phenol or of an alkylphenol thioester, and also
preferably in the presence of carbon dioxide.
. .
. .. ~ - :. . .: . . . .

201~0~
- 48 -
Other oxidation inhibitors or antioxidants useful
in this invention comprise oil-soluble copper compounds.
The copper may be blended into the oil as any suitable oil
soluble copper compound. By oil soluble it is meant that
the compound is oil soluble under normal blending
conditions in the oil or additive package. The copper
compound may be in the cuprous or cupric form. The copper
may be in the form of the copper dihydrocarbyl thio- or
dithio-phosphates. Alternatively, the copper may be added
as the copper salt of a synthetic or natural carboxylic
acid. Examples of same thus include ClO to C18 fatty
acids, such as stearic or palmitic acid, but unsaturated
acids such s oleic or branched carboxylic acids such as
napthenic acids of molecular weights of from about 200 to
500, or synthetic carboxylic acids, are preferred, because
of the improved handling and solubility properties of the
resulting copper carboxylates. Also useful are oil-soluble
copper dithiocarbamates of the general formula (RR,NCSS)nCu
(where n is l or 2 and R and R, are the same or different
hydrocarbyl radicals containing from 1 to 18, and
preferably 2 to 12, carbon atoms, and including radicals
such as alkyl, alkenyl, aryl, aralkyl, alkaryl and
cycloaliphatic radicals. Particularly preferred as R and
R, groups are alkyl groups of from 2 to 8 carbon atoms.
Thus, the radicals may, for example, be ethyl, n-propyl,
i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl,
i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl,
2-ethylhexyl, phenyl, butylphenyl, cyclohexyl,
methylcyclopentyl, propenyl, butenyl, etc. In order to
obtain oil solubility, the total number of carbon atoms
(i.e., R and R,) will generally be about 5 or greater.
Copper sulphonates, phenates, and acetylacetonates may also
be used.
Exemplary of useful copper compounds are copper
CuI and/or CuII salts of alkenyl succinic acids or
anhydrides. The salts themselves may be basic, neutral or
:: . . . , ~ : . : .
- . .: . . : .
: . . . . ...
`. " , .
' ~
.

201~0~3
- 49 -
acidic. They may be formed by reacting (a) polyalkylene
succinimides (having polymer groups of Mn of 700
to 5,000) derived from polyalkylene-polyamines, which have
at least one free carboxylic acid group, with (b) a
reactive metal compound. Suitable reactive metal compounds
include those such as cupric or cuprous hydroxides, oxides,
acetates, borates, and carbonates or basic copper
carbonate.
Examples of these metal salts are Cu salts of
polyisobutenyl succinic anhydride, and Cu salts of
polyisobutenyl succinic acid. Preferably, the selected
metal employed is its divalent form, e.g., Cu+2. The
preferred substrates are polyalkenyl succinic acids in
which the alkenyl group has a molecular weight greater than
about 700. The alkenyl group desirably has a Mn from
about 900 to 1,400, and up to 2,500, with a Mn of about
950 being most preferred. Especially preferred is
polyisobutylene succinic anhydride or acid. These
materials may desirably be dissolved in a solvent, such as
a mineral oil, and heated in the presence of a water
solution (or slurry) of the metal bearing material.
Heating may take place between 70. and about 200 C.
Tempsratures of 110C to 140C are entirely adequate. It
may be necessary, depending upon the salt produced, not to
allow the reaction to remain at a temperature above about
140'C for an extended period of time, e.g., longer than 5
hours, or decomposition of the salt may occur.
The copper antioxidants (e.g., Cu-polyisobutenyl
succinic anhydride, Cu-oleate, or mixtures thereof) will be
generally employed in an amount of from about 50 to 500 ppm
by weight of the metal, in the final lubricating or fuel
composition.
Friction modifiers serve to impart the proper
~riction characteristics to lubricating oil compositions
such as automatic transmission fluids.
- - .
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. - . ~ : :
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- 50 -
Representative examples of suitable friction
modifiers are found in U.S. Patent No. 3,933,659 which
discloses fatty acid esters and amides; U.S. Patent No.
4,176,074 which describes molybdenum complexes of
polyisobutenyl succinic anhydride-amino alkanols; U.S.
Patent No. 4,105,571 which discloses glycerol esters of
dimerized fatty acids; U.S. Patent No. 3,779,928 which
discloses alkane phosphonic acid salts; U.S. Patent No.
3,778,375 which discloses reaction products of a
phosphonate with an oleamide; U.S. Patent No. 3,852,205
which discloses S-carboxyalkylene ~ydrocarbyl succinimide,
S-carboxyalkylene hydrocarbyl succinamic acid and mixtures
thereo~; U.S. Patent No. 3,879,306 which discloses
N(hydroxyalkyl)alkenyl-succinamic acids or succinimides;
U.S. Patent No. 3,932,290 which discloses reaction
products of di- (lower alkyl) phosphites and epoxides; and
U.S~ Patent No. 4,028,258 which discloses the alkylene
oxide adduct of phosphosulfurized N-(hydroxyal~yl) alkenyl
suc¢inimides. The most preferred
friction modifiers are succinate esters, or metal salts
thereof, of hydrocarbyl substituted succinic acids or
anhydrides and thiobis-alkanols such as described in U.S.
Patent No. 4,344,853.
Pour point depressants, otherwise known as lube
oil flow improvers, lower the temperature at which the
fluid will flow or can be poured. Such additives are well
known. Typically of those additives which usefully
optimize the low temperature fluidity of the fluid are
C8-C18 dialkylfumarate vinyl acetate copolymers,
polymethacrylates, and wax naphthalene. Foam control can
be provided by an antifoamant of the polysiloxane type,
e.g., silicone oil and polydimethyl siloxane.
Anti-wear agents, as their name implies, reduce
wear of metal parts. Representatives of conventional
antiwear agents are zinc dialkyldithiophosphate and zinc
diaryldithiosphate.
A
. . ~
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- . . . . . . .
~. . .

-- 51 --
Detergents and metal rust inhibitors include the
metal salts of sulphonic acids, alkyl phenols, sulfurized
alkyl phenols, alkyl salicylates, naphthenates and other
oil soluble mono- and di-carboxylic acids. Highly basic
(viz, overbased) metal salts, such as highly basic alkaline
earth metal sulfonates (especially Ca and Mg salts) are
frequently used as detergents. Representative examples of
such materials, and their methods of preparation, are found in
Canadian Patent No. 1,262,721 issued November 7, 1989.
Some of these numerous additives can provide a
multiplicity of effects, e.g., a dispersant-oxidation
inhibitor. This approach is well known and need not be
further elaborated herein.
Compositions when containing these conventional
additives are typically blended into the base oil in
amounts which are effective to provide their normal
attendant function. Representative effective amounts of
such additives.are illustrated as follows:
Additive Wt.% a.i. Wt. % a.i.
(Broad) (Preferred)
Viscosity Nodifier .01-12 .01-4
Corrosion Inhibitor 0.01-5 .01-1.5
Oxidation Inhi~itor 0.01-5 .01-1.5
Dispersant 0.1-20 0.1-8
Pour Point Depressant 0.01-5 .01-1.5
Anti-Foaming Agents 0.001-3 .001-0.15
Anti-Wear Agents 0.001-5 .001-1.5
Friction Modifiers 0.01-5 .01-1.5
Detergents/~ust Inhibitors .01-10 .01-3
Mineral Oil Base Balance Balance
When other additives are employed, it may be
desirable, although not necessary, to prepare additive
concentrates comprising concentrated solutions or
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:

2~1~0~3
dispersions of the multifunctional viscosity improver (in
concentrate amounts hereinabove described), together with
one or more of said other additives (said concentrate when
constituting an additive mixture being referred to here in
as an additive package) whereby several additives can be
added simultaneously to the base oil to form the
lubricating oil composition. Dissolution of the additive
concentrate into the lubricating oil may be facilitated by
solvents and by mixing accompanied with mild heating, but
this is not essential. The concentrate or additive-package
will typically be formulated ~o contain the dispersant
additive and optional additional additives in proper
amounts to provide the desired concentration in the final
formulation when the additive-package is combined with a
predetermined amount of base lubricant. Thus, the products
of the present invention can be added to small amounts of
base oil or other compatible solvents along with other
desirable additives to form additive-packages containing
active ingredients in collective amounts of typically from
about 2.5 to about 80%, and preferably from about 5 to
about 60%, and most preferably from about 8 to about 49% by
weight additives in the appropriate proportions with the
remainder being base oil.
The final formulations may employ typically about
wt. % of the additive-package with the remainder being
base oil.
All of said weight percents expressed herein are
based on active ingredient (a.i.) content of the additive,
and/or upon the total weight of any additive-package, or
formulation which will be the sum of the a.i. weight of
each additive plus the weight of total oil or diluent.
The instant compositions of matter useful as
multifunctional viscosity modifiers or improvers are
oil-soluble, dissolvable in oil with the aid of a suitable
solvent, or are stably dispersible materials. Oil-soluble,
dissolvable, or stably disparsible as that terminology is
.
, : ~
. - . . . .

201~063
- 53 -
used herein does not necessarily indicate that the
materials are soluble, dissolvable, miscible, or capable of
being suspended in oil in all proportions. It does mean,
however, that the additives, for instance, are soluble or
stably dispersible in oil to an extent sufficient to exert
their intended effect in the environment in which the oil
is employed. Moreover, the additional incorporation of
other additives may also permit incorporation of higher
levels of a particular copolymer hereof, if desired.
The following Examples further illustrate the
instant invention. They are presented by way of
illustration and not limitation. Unless otherwise
indicated, all parts and percentages are on a weight basis.
The following examples illustrate the preparation
of amido-amines of the instant invention.
EXAMPLE 1
Into a reactor vessel are charged 148 grams (2
moles) of 1,3-propane diamine and stirred at room
temperature under a nitrogen atmosphere. 86 grams (one
mole) of methyl acrylate are slowly introduced into the
reactor vessel while keeping the resulting reaction mixture
below 50C. After the methyl acrylate addition is complete
the reaction mixture is heated at 80C until infrared
analysis shows the absence of the ester bond. The reaction
mixture is then stripped at 80~C for one hour to distill
off the methanol byproduct. Analysis of the resulting
amido-amine product indicates 9.93 meq. of primary nitrogen
per gram of sample and 27.64% nitrogen.
EXAMPLE 2
The procedure of Example l is repeated except that
the 148 grams of 1,3-propane diamine are replaced with 203
grams (2 moles) of diethylene triamine. Analysis of the
resulting amido-amine product indicates 4.48 meq. of
primary nitrogen per gram of sample and 25.85% nitrogen.

2015063
- 54 -
EXAMPLE 3
The procedure of Example 1 is repeated except that
the 148 grams of 1,3-propane diamine are replaced with 292
grams (2 moles) of triethylene triamine. Analysis of the
resulting amido-amine product indicates 3.67 meq. of
primary nitrogen per gram of sample and 26.76% nitrogen.
EXAMPLE 4
The procedure of Example 1 is repeated except that
the 148 grams of 1,3-propane diamine are replaced with 378
qrams (2 moles) of tetraethylene pentamine. Analysis of
the resulting amido-amine product indicates 4.3g meq. of
primary nitrogen per gram of sample and 28.3% nitrogen.
The following Examples illustrate the preparation
of the nitrogen containing carboxylic acid material grafted
ethylene propylene copolymers of the instant invention.
EXAMPLE 5
Into a reactor vessel are charged 200 grams of a
wt. % oil solution of succinic-anhydride grafted
ethylene-propylene copolymer (containing about 43 wt.%
ethylene and 57~ wt.% propylene, the ethylene-propylene
bac~bone having a ~n of about 80,000, and having a
thickenlng efficiency of about 1.2), 21.3 grams of
polyisobutenyl succinic anhydride (having a succinic
anhydride to polyisobutenyl mole ratio of 1.04, a
polyisobutylene ~n f about 960, ASTM
Sapon~fication Number of 112, and 90 wt.% active
lngredient, i.e., polyisobutenyl succinic anhydride, the
remainde~ being primarily unreacted polyisobutylene), and
130 grams of S130N mineral oil. The reactor vessel is
blanketed with nitrogen and heated to 175C for one-half
hour. To this reactor vessel are then added 4.12 grams of
~mldo-amine prepared in accordance with the procedure of
Example 1. The reaction mixture is nitrogen stripped for 3
hours at 175C. At the end of this period the reaction
mlxture is cooled to lOO~C and is discharged from the
reaction vessel.
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- 55 -
EXAMPL~ 6
The procedure of Example 5 is repeated except that
the 4.12 grams of the amido-amine prepared in accordance
with the procedure of Example 1 are replaced with 9.02
grams of amido-amine prepared in accordance with the
procedure of Example 2.
EXAMPLE 7
The procedure of Example 5 is repeated except that
the 4.12 grams of the amido-amine prepared in accordance
with the procedure of Example 1 are replaced with 11.0
grams of amido-amine prepared in accordance with the
procedure of Example 3.
EXAMPLE 8
The procedure of Example 5 is repeated except that
the 4.12 grams of the amido-amine prepared in accordance
with the procedure of Example 1 are replaced with 9.2 grams
of amido~amine prepared in accordance with the procedure of
Example 4.
Thickening efficiency (T.E.) is defined as the
rati.o of the we~ght percent of a polyisobutylene (sold as
an oil solution by Exxon Chemical Company as Paratone N~,
having a Staudinger molecular weight of 20,000, required to
thicken a solvent-extracted neutral mineral lubricating
oil, having a viscosity of 150 SUS at 37.8C, a viscosity
index of 105 and an ASTM pour point of 0F. (Solvent 150
Neutral) to a viscosity of 12.4 centistokes at 98.9C to
the weight percent of a test copolymer required to thicken
the same oil to the same viscosity at the same
temperature. For linear polymers of a given ethylene
content, the thickening efficiency is approximately
proportional to the 0.75 power of the weight-average
molecular weight.
TM - ~rade mark
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.
.