CA1069878A - Dispersant and v.i. additives for lubricants - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Copolymers of ethylene and a C3 to C18 straight or branched chain.
.alpha.-olefin, or terpolymers of ethylene, a C3 to C18 .alpha.-olefin and a C5 to C12 non-conjugated diolefin, or mixtures thereof, are dissolved in a mineral lubricating oil, and the solution oxidized with air or an oxygen-containing gas. The oxidized solution, in which both the polymer and the oil have been oxidized, is reacted with an amine compound to form a polyaminox composition having utility as a dispersant additive for lubricants. When made from high molecular weight polymers, the polyaminox composition is useful as a multi-functional dispersant-viscosity index improver additive for lubricants.

Description

~ 10~8'7~3

2 IELD OF THE_INVENTION

3 This invention is concerned with processes and prod- -

4 ucts resulting from the reaction of amlne compounds with,(a) oxidized oll solutions o~ copolymers of ethylene with one or 6 morec~-olefins; (b3 oxidized oil solutions o~ terpolymers 7 of ethylene, one or moreO~-ole~ins9 and one or more non-8 con~ugated diole~ins; and (cj oxidized oil solutions of mix-9 tures o~ said copolymers and/or terpolymers. The oxidized polymer in oil-amine reaction prod1lcts9 hereina~ter identi-11 fied a~ "polyaminox" productsg impart improved detergency 12 and dispersant properties when cvmpounded i~ lubrican~s~ and 13 can also act as viscosity lndex improvers when made from high 14 molecular weight polymers.
PRIOR ART
_ 16 A variety of compositions comprising polymeric or 17 high-molecular weigh~ materials whlch incorporate nitrogen 18 have been described in U-S- and fore1gn p~tents as disper-19 sants ~or fuels and lubricants, and as vi~cos~ty index im~
provers for lubricants. For exampleO
21 U.S. Patent 393169177 teaches reaction of poly~
22 amine with the reaction product of maleic anhydride with an 23 oxidized interpolymer o~ ethylene and propylene9 as a sludge 24 dispersant in lubricant and fuel compositionsO
U.S. Patent 3,4049091 describes the preparation o~
26 nitrogen containing polymers, useful as sludge dispersants 27 and viscosity index improversg by grafting polar monomers 28 such as acrylonitrile onto hydroperoxidized ethylene-pro-29 pylene copolymers.
U.S. Patent 3~404,092 describes the preparation of 31 polymeric visco~ity index improvers containing urethane 32 groups by the reaction o~ hydroxylated ethylene~propylene 33 copolymers with isocyanate~.

7~
1 U.S~ Patent 39687,849 descrlbes ~he preparation of 2 viscosity index improvers, pour point depressants and di~-3 persants, for ~uels and lubricants, by grafting various un-4 saturated monomers onto a degraded~ oxidizedJ lnterpolymer o~ ethylene and propylene.
6 U.S. Patent 3,687,905 descrihes the preparation o~
7 addi~ives for fuels and lubricants by the reaction of an un-8 saturated acid, such as maleic acid or anhydride, with an oxl-9 dized, degraded interpolymer of ethylene and propylene9 fol-lowed by reaction with a polyamine.
11 British Patent 983,o40 describes the preparation 12 of detergent additives for lubrlcants by the react~on of a 13 polyamine with a long chain monocarboxylic acid prepared by 14 oxidation of an ole~in polymer.
British Patent 1~027,410 describes the preparation 16 of ashless detergents ~or lubricating oils by the reaction 17 o~ a polyhydroxyamine with a polymeric monocarboxylic acidO :
18 British.Patent 19172,818 describes the preparation 19 of additives for lube oils by th~ cond.ensation o~ an amine with an ozonized polymer.
21 ~erman Seria~ 2,2079434 discloses the preparation ` 22 o~ lube oil additlves by the condensation of an amine with 23 an oxidized ethylene-propylene copolymergprepared by air blow-24 ing in the presence of a peroxide (also see U.S. Patent 3>785,980),or by mastication of the polymer in the presence 26 o~ oxygen (also see U.SO Patent 39769~216). ~:

28 In distinction to the products and processes o~
; 29 the prior art~ we have now found that diæpersants for lubri-cants, and multifunctional dispersant v1scosity index im-31 provers for lubricantsJ may be prepared by the reaction 32 of amine compounds with oxidized oil æol.utions of copolymers 33 of ethylene and one or more c~-oleflnsg or oxidized oil ` : :

'78 1 solutions o~ terpolymers of ethylene~ one or more ~-ole-2 fins and one or more non-con~ugated diole~ins, or oxidized 3 oil solutions of mixtures Or said copolymers and/or terpoly-4 mers. Thls invention further encompasses processes ~or the production of the polyaminox reaction products o~ th~s in-6 vention,and compositions comprising a maJor proportion o~
7 a hydrocarbon fuel,or lubricant,and a minor propor~ion of 8 said polyaminox product.
9 By carrying out th~e oxidation o~ the polymer ln an oil solution, the handling and oxidation of the polymerj 11 particularly when the polymer is of high molecular weight, 12 is facDltated~ While some of the prior art oxidation pro-13 cesses used inert solventsg the solvent was usually later 14 removed by evaporation. On the other hand, the present in-~ention uses a high boiling oil as the polymer solvent9 which 16 oil is not removed after oxidation and amlnatl~n9 but rather 17 can be added to the finished composition9 e.g., a crankcase 18 lubricant composition, even tnough the oil has also become 19 oxidized and probably aminated to some extent. Thus, a sizable portion, e.g., as much as 10 or 20~9 of the final 21 lubricant product ready for crankcase or engine use~ can 22 comprise oil that has been oxidized9a.~d good results can 23 st~ll be obtained in engine performance, This was unex 24 pected because oxidized products present in the crankcase lube oil,and coming either from the oil or gasoline9 would 26 be expected to contribute materially to formation of acid, 27 wear, varnish and to promote the formation of sludgeO Yet~
28 the oxidized and aminated polymer~n-oil solution appears 29 very effective in engine operationO
In greater particularity, this invention relate~
31 to oil solutions o~ Zlegler-Natta catalyzed copolymers of 32 from 30 to 80 weight percent o~ ethylene and one or more C3 -~06~878 l to Cl8, pre~erably C3 to Cg, straighk or b~anched chain 2 acyclicd~-olefins; or oil solutions o~ Ziegler-Natta cata-3 lyzed terpolymers o~ from 30 to 80 weight percent o~ ethylene, 4 one or more C3 to Cl8,pre~erably C3 to C8, straight or branched chaln acyclic orcC~-ole~ins and up to 15 weight per-6 cent of one or more C5 to Cl2 acyclic or alicyclic non-con-7 ~ugated diolefins; and to oll solutions of mixtures of said 8 copolymers and/or terpolymers, which have been oxidized with 9 air, or oxygen containing gas, and then reacted with an amine compound to ~orm a polyaminox comp~sition.
11 Most particularly, this invention rel~tes to poly-12 aminox compos~tions and the processes for their preparation 13 ~n which9 generally:
14 (a) the oil used for solubilizing the copolymers9 15 terpolymers and mixtures thereof9 prior to oxidation with ~ :
16 air or oxygen containing gas, may be a lubricating oil, 17 which may be a deasphalted, dewaxed9 acid treated0 sorbent 18 treated or solvent extracted petroleum distillate, raf~inate~ . .
19 or ole~in polymerized synthetic oll9 having a viscosity in 20 range o~ about 50 to 1000 SUS @ 100F.9 preferably 70 to ~-21 600 SUS @ 100Fo~ most preferably 80 to 200 SUS @ 100F.;
22 (b) the relative proportions of said olefin mono~ :
23 mers in the polymer will generally be as follows:
30 to 80, preferably 40 to 70 wt. % ethylene 2~ 70 to 20, preferably 60 to 30 wt. % C3-l8 26 . olefin andg 27 0 to 15, preferably 3 to lO wt~ % diolefin;
2~ (c3 the number average molecular weight (~n)f 2g said copolymers and terpolymèr~ is-in the range of about 500 to 500,000, more preferably lO00 to 1009000, most prefer-31 ably 1500 to 809000;
32 (d) the concentration o~ polymer in oil when oxi-33 dation i5 commenced 1~ in the range o~ about 0.5 to 90 weight ~ 5 ~

1 percent, preferably 2 to 50 weight percent, based on the 2 total weight of polymer and oil;
3 (e) the temp~rature at which the ox~da~ion is 4 conducted is in the ranKe o~ about 80~C~ to 300C., prefer-ably 100C. to 230C.;
6 (f) oxidation is conducted ~or a time sufficient 7 to impart a combined oxygen content in the range of about 8 0.01 to 10.0, e.g. 0.1 to 8, preferably 0.1 to 5.0 weight 9 percent~ based on the total weight of the oil-polymer solu-tion;
11 (g) reaction of the oxidized oil-polymer solution 12 is with an amine compound, preferably selected from the group 13 consisting of nitrogen compounds having the general Pormulae:
R-N-RI; R-N (CH2)s~[~N(CH2)s~t l 16 R' Rl H R' 17 ~H2 CH
18 2 2 P `CH2 _ CH2 wherein Rg Rl and R" are independently selected from the 21 group consisting of hydrogen; Cl to C12 straight or branched 22 chain alkyl radicals; Cl to Cl alkoxy C2 to C6 alkylene 23 radicals; C2 to C12 hydroxy-alkylene radicalsg C2 to C12 24 aminoalkylene radicals; Cl to C12 alky~mino C2 to C6 alkylene radicals; G is independently selected from the group consist-26 ing of hydrogen and ~-amino- alkylene radicals of from 1 to 27 3 carbon atoms; s is a cardinal number o~ from 2 to 6; t is 28 a cardinal number of from 0 to 10, and p is an integer of .
29 ~rom 1 to 4;
(h) amination~ i~e. reaction o~ the amine compound ~ 31 with the oxidized oil-polymer solution, is conducted at a 32 temperature in the range of about 40C. to 300C., preferably 33 at a temperature of 100C. to 200C., and 1 (1) a ~ o~ ~mine compound to oxygen in 2 the oxidized oil-polymer solution of about 0.01 to l.o, e.g., 3 0.1 to 1.0, mole~ o~ amine compound, preferably O.Z ~o 0~5 4 moles of amine compoundJ per mole o~ oxygen present in the oxidized oll-polymer solut~on.
6 When the polyaminox products of this invention are 7 prepared from Ziegler~Natta copolymers and terpolymers laving 8 a ~n in the range of 500 to 20,000, pre~erably 800 to 1090009 9 they are particularly effective and useful as dispersants.
When the polyaminox products are prepared from similar poly-11 mers having a ~n in the range of about 11,000 to 5009000 pre- -12 ferably 20,000 to 100,000, they are particularly useful as 13 dispersants and as viscosity-index improvers.

, .
Polymers 16 Copolymers o~ ethylene and one or more C3 to Clg 17 c~-olefins; and terpolymers of ethylene9 one or more C3 to 18 Clg c~-olefins, and one or more C5 to C12 non-con~ugated d~
19 olefins; suitable for the pract~ce of this invention9 uslng Ziegler-Natta catalysts, har~e been extensively studied and 21 reported in the patent and scientific literature. See for 22 example: "Polymer Chemistry of Synthetic Elastomers"9 edited 23 by Kennedy and Tornqvist, Interscience Publishers9 ~.Y. 1969 ~ -24 and Baldwin and Ver Strate: "Polyolefin Elasto~ers ~ased on Ethylene and Propylene", Rubber Chem. & Tech, 459 790-881 26 (lg72).
27 Copolymers of ethylene and one or more C3 to C18 28 c~-olefins which may be utiliæed to prepare the polyamlnox 29 products of this invention may compri~e from 30 to 80 weight percent of ethylene and a single C3 to Clg straight or branched 31 chain o~olefin such a~ for example: propylene,l-butene91-32 pentene, l~hexene, 5-methyl-1-penteneJ l-decene,397-dlmethyl 33 l-octene, l-dodecene, l-tridecene, l-hexadecene and 1 octa~

~LO~ '7~
1 decene, or mixtures thereof; or a mixture of odd and even 2 numberedo~-olerins such as are obtalned by steam-cracking 3 of deolled paraffln wax; or a mixture of even nu~bered c~
4 ole~ins such as are obtained by the dehydration of mixed fatty alcohols obtained from hydrogenated fats; or Ziegler 6 growth alcohols using ethylene; orc~-olefins obtained by the 7 oligomerization of ethylene; etc~ C3 to C8 cX~oleflns are 8 preferredJ and propylene is most preferred.
9 Also suitable, are mixtures of copolymers of eth~
ylene with individual c~-olefins in the C3 to C1g range, mix-11 tures of terpolymers havin~ the same or different c~olefins 12 and diolefins but differing in monomer content, and mixtures 13 of said copolymers and terpolymers.
14 Particularly suitable, for a V.I. effect are co~
polymers and terpolymers having a high ethylene content9 for 16 example 60 to 80, preferably 65 to 75 wt. % ethylene, and 17 which may be 3 to 25, e.g., 5 to 10 wt. % crystalline9 as gen-18 erally they giveagr~er V.I. effect. These high ethylene 19 polymers can be used per se, or frequently can be blended to advantage with low e~hylene content (e.g., 35 to 50 wt. % eth-21 ylene) polymer which in itself gives a good V.I. effect,either 22 before, or after, oxidation on amination to make the products 23 of the invention.

~5 26 In many cases, the terpolymers, especially those 27 with at- least 3 or 4 wt. % diene are preferred, as the unsat-28 uration in the diene, outside the backbone o~ the polymer, 29 is believed ko preferentially oxidize9 thereby providing many points ~or subsequent amination, wlthout undue chaln 31 breakage and 10SB o~ molecular welght and thickening ef-32 ficiency.

33 The catalyst composikions for the preparation o~

.. .. . .. _ .. ...

~.06987~3 1 copolymers and terpolymers) will generall~ comprise a prin~
2 cipal catalyst consisting of a transition metal cornpound 3 from Groups IVb, Vb and ~Ib of the Periodic Table o~ ~he 4 Elements, particularly compounds of titanium and vanadium~
and organometallic reduclng compounds from Groups IIa, IIb 6 and IIIa, particularly organoaluminum compounds, which are 7 designated as cocatalysts.
8 Preferred principal catalysts of vanadium have the g general formula VOzXt wherein z has a value of ~ero or one and t has a value of 2 to 4. X is independentl~ selected 11 from the group consisting o~ halogens having an atomic num-12 ber equal to or greater than 179 acetylacetonates, halo-13 acetylacetonates, alkoxides and haloalkoxides. Non-limiting 14 examples are: VOC13i VOC12(0Bu); VO(~cAc)2; VOC12(Ac~c); and V(AcAc)3, where Bu is a n-butyl or isobutyl alkyl radical and 16 (AcAc) is an acetylacetonate.
17 Preferred cocatalysts have the general ~ormula 18 AIR"mX'n wherein R" is a monovalent hydrocarbon radical se- -19 lected from the group consisting of Cl to C12, alkyl,alkyl-aryl~ arylalkyl and cycloalkyl radicals, X' is a halogen 21 having an atomic number equal to or greater than 17~ m is 22 a number ~rom 1 to 3, and the sum of m and n is equal to 23 three~ Non-limiting examples of useful cocatalysts are:
24 Al(Et)3; Et2AlCl; EtAlC12; Et3A12C13; and Al(isoBu) Representative non-limiting examples o~ non-con-26 Jugated dienes useful as monomers for the preparation of 27 suitable terpolymers include:
28 A. Straight-chain acyclic dienes such as 1,~-29 hexadiene; 1,5-heptadiene; and 1,6-octadiene.
B7 Branched-chain acycllc dienes such as 5-methyl-31 1,4-hexadiene; 3,7-dimethyl-1, 6-octadiene; 397-dimethyl-l, 32 7-octadie~e; and 8-methyl-1, 7-nonadiene.

_ g _ 1 C, Single ring alicyclic dienes such as: 1,4-2 cyclohexadiene; 1,5-cyclo-octadiene; 1,5-cyc~odecadiene;
3 4-vinylcyclohexene; 4-methylene cyclohexene; 4-ethylidene 4 cyclohexene; 1 allyl-4-isopropylidene cyclohexane; 3-allyl-cyclopentene; 4-allylcyclopentene; and 1-isopropenyl-4(4-6 butenyl) cyclohexane~
7 D. Multi-single ring alicyclic dienes such as:
8 4,4'-dicyclopentenyl and 4,4'-dicyclohexenyl. .
9 E. Multi-ring alicyclic fused and bridged ring dienes such as: tetrahyd.roindene, methyltetrahydroindene;
11 dicyclopentadiene, bicyclo(2,291) hepta-295-diene; alkenyl 12 alkylidene; cycloalkenyl and cycloalkylidene norbornenes 13 such as: 5-methylene-2-norbornene; 5-ethylidene-2-nor~ornene;
14 5-methylene-6-methyl-2-norbornene; 5-methylene-6, 6-dimethyl-2-norbornene; 5-propenyl-2-norbornene; 5-isopropylidene 2-16 norbornene; 5-(3-cyclopentenyl)-2-norbornene, and 5-cyclo-17 hexylidene-2-norbornene.
18 Commercially available terpolymers3 produced 19 mainly for use in elastomeric compositions, which are suitable for the practice o~ this invention may be illustrated for 21 a number of non-con.jugated diolef~ns in which the monomer 22 moieties in the terpolymer are linked in the polymer chain 23 in a random sequence and vary~ng number as follows:

CH2-CH2~ ~ CH2-CHty ~ cH_cH2~,~vv~v~
26 CH3 CH CH=C~-CH3 27 Ethylene Propylene 1,4-Hexadiene 28 Units Units Units _ 10 -;;91378 1 2. H H
4 ~ CH2-C~ C c~Z~ CH2-CH2~--~ HÇ ~
9 HC C~I/ 2 Propylene Dicyclopentadiene Ethylene 11 Units Units Units , . ~, .

12 3. H H ~ -1~ ~ CH2-CH2 ~ C--C\z ~ CH-CH
16 HC\ CH2 / N 3 ~ N2C - C=CH CH3 19 Ethylene 5-Ethylidene-2-Nor- Propylene Units bornene Units Units wherein x, y and z are integer, typically in the range of 21 1 to 20~ It will be understood that the sequence of monomer 22 enchainment is random and that the numerical values assigned 23 to x, y and z are not necessarily totals for any monomer in 24 the terpolymer but that these values express the number o~
25 t~mes a given monomer may be repeated in the polymer chain - ;
26 before another monomer is interposed in the chain.
27 While these copolymers and terpolymers are essen-28 tially amorphous, they may contain up to 25 percent by weight 29 of crystalline segments as determined by X-ray or differen-tial scanning calorimetry. Details of these methods ~or 31 measurement of crystallinity are found in Journ. Polymer 32 Sci. A-2, 9, 127 (1971) by Go Ver Strate and Z.W, Wilchinsky.
33 Synthesis of the copolymers and terpolymers use~ul .
34 in the practice o~ this invention may be conducted in a slurry process utilizing non-solvents such as methyl chloride 36 or methylene chloride, or in a solution process utilizing 37 solvents such as hexane, heptane, and toluene, in batch, ~ , .. . .

3L0~ 713 1 ~taged or continuou~ reactors. Polymer made in ~ ~olu~io~
2 process is preferred, since the polymer cement, either be-3 ~ore ~r after deashing, may be mixed or fluxed w~th the oil to form a solution which is to be oxidized, and the solvent and any unreacted residual monomers recovered, ~or example9 6 by stripping with vacuum, nitrogen or steam.
7 Solvents utilized in the synthesis should be free 8 o~ moisture and catalyst poisons such as merCaptans and 9 acetylene compounds, and the reaction milieu, which is pre-ferably blanketed with an oxygen-free gas such as nitrogen 11 or methane, should be free of moisture, air or oxygen and 12 catalyst poisons such as carbon monoxide~
13 Solvent, monomers, principal catalyst and cocat-14 alyst are fed to the reactor, supplied with means ~or with-drawal of the heat of reactionj and maintained under con-16 trolled agitation ~or a time, temperature, concentration 17 and pressure sufficient to complete the reaction or ensure 18 a steady-state equilibr~um.
19 Suitable times of reaction will generally be in the range of from about 1 to 300 minutes, temperature will 21 usually be in the range of 0C. to 100C. and pressures from 22 atmospheric to 160 psig may be employedc Monomers fed to 23 the reactor per 100 parts by weight of solvent may be in 24 the range of: ethylene, 2 to 20 parts by we~ht, C3 to Clg 25 C~-olefin, 4 to 20 parts by weight; and when used to pre-26 pare a terpolymer, non-con~ugated diolefin, 0 tl to 10 parts 27 by weight.
28 ~ Principal catalyst, VOC13 for example, prediluted 29 with solvent, can be ~ed to the reactor so as to provide a concentration i~ the range o~ 0.1 to 5.0 millimoles per 31 liter. Cocatalyst, for example Et3A12C13 also pred iluted 32 if desired, can be ~ed to the reactor at the same time ln an 33 amount equal to from about 2.0 to 20 moles of cocatalyst per - 12 ~
.

~ 0~ 8 mole o~ princ lpal cataïys t .
2 Copolymers ~nd terpolymer~ suitable ~or the prac-3 tice o~ thi~ invention may have number average molecular 4 welghts (~n) in the range of ~bout 500 to 500,000. The mo~
lecular weight of the polymer obtained under a given set of 6 operating conditions is influenced and regulated by the 7 choice of solvent, monomer and principal catalyst concentra=
8 tlon, the nature and amount o~ cocatalyst employed9 the tem~
g perature at which the synthesis is conducted, and the use of iO chain transfer reagents such as hydrogen,~which may be fed 11 to the reactor in an amount in the range of 10 ~o 103 000 ppm 12 of the ethylene fed to the reactor. In general~ polymers 13 having a narrow range of molecular weight9 as determined by 14 the ratio of weight average molecular weight (~w~ to(~n)are preferred. Polymers having a ~w/~n f less than 109 pre~
16 ~erably less than 7, and most pre~erably 4 or less~ are most 17 deslrable. Polymers in this range may be obtained by selec~
18 tion of synthesis conditions and addition of hydrogeng as 19 above noted, and by post synthesis treatment such asO ex~
trusion at ~evated temperature~ and under hlgh shear through 21 ~mall orifices, or by fractional precipitation from solution.
22 The properties of a number o~ random polymers and 23 random terpolymers used in the various work~ng examples of 24 the invention are summarlzed in Table I, which ~ollows:

-.

~069~

* a) ~ o ~ o~
~ ~ , , , , o o o C~ o g o g g g o o o 8 ,~ I O ~ O O O ~ ~D ~ O O O I O O
~Q 1~:, o ~ ,, ~ ~ U~
~ .. :
Hl i~~ J ~ ~ o o o ~~) o o ;~ j ~ P~1~
~1: ~ ~ ~ ~ o ~1 ~N ~ ~ ~

~ "
D ~ æ ~ ~ N .=t ~O
~ ::
h¦
~¦ ¢ m : ~
~4 :

` -, . . . . .
, ~o o d ~ X d * u~r~ ~ $ ~ ~ ~ C) P
~,~ o ,1 ooU~ o ~ d d ~i ~o o ~ cdo W g ~
0 ,~ CO
~ a ~ ~ ~ d ~.
a~ ~ c) o ~
a ~3 p \~ h ~ ~ '--1 ~
~ ~R ¦ ~ o o J- P 0 g R
O ~ u~
J_) O ~1 ~J U) ~
qe o~ d u~) O p rl O ~ u ~ a) R ~ d d I II ~ I ~ I u ~1 a) O' ~\
P 1~ ~ ~ ~ ~ h a~ O ~ , æH 0 ~ ~ ~ R P
æ a~
o ~ ~ ~ co w o w ,~ s~
- a) ~ t) o~, ,~ ~w U r e 0 .
~1 O~ 0 ~æ e~ u ,~1 u ,~ bl~ c~ h E-~ w tJ R
u ~i ~ O ~ 0 h R ~3 h .
a~ co ~ ~0 ~ h d h ~ ~r~ ~,r~ ~ O OJ O r~ h u~
!2 h 0 0 ~ 0 0 ~ ~w h R a) 0 w ~
R . ,~ p~ p, ~_ rl ~ ~ O ,~ a ~ g r~ ~1 rC) 1~ rl O~
o~ a ~ ~0 0 ~ bO ~ ;W C~l O h ~h~ c~ ~
~ ~1 ~ ~ ~ O ~E~ ~ h d E~
O P~ ~;t ~ C~l 1/') u~ 1~~1r~ h aJ ~rl o a) O h o ~ w.
~0¢ OR ~ ~0 ~w 0 1~ ~
h I ~ d .c o ~ I ~n a) ~ d tO h E I h- R ~C
~0 ~ ~0e R ,_1 ~ . p~

6> 1 O Pl O' p~ h ~ ~ d d ~ ~n ~, I ''~ UR U~
d I o ~ v~ . O O o 4~
,; , ~ u~ ~, o 0 E~ ~ O
.: I I I I

. æ #

10~8~

1 A~ ~een, Table I indicate~ a wide range o~ eth-2 ylene-propylene copolymers, (Polymers H to J and M to P);
3 as well as terpolymers of ethylene and propylene with eikher 4 5~ethylidene-2-norbornene (Polymers A to G, K, L, Q and S to U), or hexadiene (Polymer R)~ Some of these polymers are 6 commercially available. Speclfically~ Polymers A, K, ~ and 7 S are available as Vistalon 2504, Vistalon 6505, Vistalon 8 3708 and Vistalon 4608, respectively, ~rom the Exxon Chemical (l~lsfa/9~ 1S a-fradt jnarJ~
~, 9 Co., while Polymer R is available as Nordel 132~. The other polymers of Table I were experimental polymers made by con-11 ventional techniques.
12 Solvent Oils For Dissolving The Polymer 13 A wide variety of mineral lubricating oils which 14 widely rang~ in viscosity and crude source, may be used as solvents for the polymer-oil solutions to be oxidized. The 16 oils may be derived from Pennsylvania, Midcontinent or 17 Coastal crudes~ Middle East crudes, Venezuelan crudes, etc., 18 and may range in viscosity from about 5 to 1000 SUS ~ 100Fog 19 preferably 10 to 600 SUS @ 100F., most preferably 80 to 200 20 SUS ~ 100Fo They may be straight-run distillates in the 21 lubricant range, e.g., boiling above 600~., or may have 22 been further refined by deasphalting~ dewaxing; lightly or 23 intensively treated with reagents such as aluminum chloride, 24 98% H2S04 or oleum containing 20~ S03; solvent extracted wlth reagents such as phenol9 furfural or sulfur dioxide; treated 26 with sorbents such as bauxite and Attapulgus clay; or re-27 ~ined by hydrogenation; etc. Also suitable are synthetic 28 hydrocarbon oils in the lubricant range made by polymeriza-29 tion9 oligomerization, alkyIation o~ aromatic~ with olefins, and the like. Pre~erred, because they generally appear to 31 glve les~ unde~irable by~product~ dur~ng oxidation, e.g., 32 color bodies, are oil~ having a ~ulfur con~ent of less than _ - 16-~)6~1~'7~
1 0.25 weight percent, e.g., as determined by X~ray fluoro-2 scopy), a nitrogen content o~ less than 25 microgram~ per 3 ml., e~g., as determlned by microcoulometry; and ~n aro~
4 matic content o~ less than 30 weight percent, e.g~, as de-

5 termined by I.R.) i.e., inf rared spectroscopyO

6 Inspections on a number of such mineral lubrica-

7 ting oils are given in Table II whlch follows:

~0f~8~

h o ~t i 0~ ~ ~ ~

O ~ J O
H
h ~ O o N
~:1 ~ Q~ ~
:~ ~ ~ ¢
æ
:~ a3 E~ I ~
~ o ~ e H ~ ~.rl ~) N
1~ ¢ O ~ ~ I o O N ~ _ cC a) ~:

H ~ h C`.l N C~ CO N
H O H ~ o +
H ~; O z N O ~1 ~1 H
~ ¢
E I ~QlP ~ ~) ~ ~ O

a) h N 2 s ~
~: o ~ C~J + o , ~ ml , ~ ~ N + N H ~_ H ¢l rl rl . I Oh O h. O h O
~.o ~
o I ~ ~ -~ I
h h h ~
, o o ~ H
O O O'S rl ~ L ~
o 0~ ,, ~, @) @) I .. nS 1~ O ~rlbR, Qh h O bD El ~1 1 s I O o n~ ~s nl c~ ~ h ~ ~ ~ h h o ~ ~
O E~ ~ P ¢ u~
N ~ 1~ 0 O~ O~ ~ ~ ~ :$ ~ ~ ~ ~ ~ N

~0~S~8'78 1 As ~een in Table II, Oil A wa~ a white oil9 Oils 2 B to E were Solvent 100 Neu~ral Oils, l.e., neu~ral oils 3 prepared by solvent extraction (phenol extrac~ion) ~rom 4 paraffinic crudes and having a viscosity of about 100 to 115 SUS at 100F. Oil F was a mixed Solvent Neutral Oil 6 and an Aromatic Oil. Oil F had a viscosity of about 158 7 SUS at 100F. Oil G was a hydro~ined naphthenic oil9 while

8 Oil H was a solvent extracted naphthenic oil of about 75

9 SUS at 100F.
Oxidation of the Oil-Polymer Solution .
11 Oxidation of the copolymers and terpolymers dis 12 solved in the oil is conveniently carried out9 ei-ther ln 13 batches or continuously, in a stirred reactor with air9 or 14 air prediluted with an inert gas such as nitrogen or carbon d~oxide 60 as to m~nimize explosion hazards. The air9 or 16 d~luted air, may be introduced into the oil-polymer solution 17 in a finely divided state through the use, for example9 of 18 sparger tubes fitted with porous ALUND ~ 9 or fr~tted glass 19 thimbles, or similar means possessing a forminiferous like structure, at a temperature in the range o~ about 80Co to 21 300C., preferably 100C. to 230C, Rap~d agitation of the 22 reactor contents, as for example, by means of a turbomixer 23 is desirable in large batches, to ensure an optimum reaction 24 rate and a low oxygen content in the off-gas.
In general, in the range of 0.5 to 90, e.g. 9 4 to 26 60 weIght percent of the oil-polymer solution will be poly~
27 mer. Usually, about 20 to 60 weight percent of the solution 28 will be polymer when the polymer is of low mol. wt 7 9 e.g. 9 2~ with a number average molecular weight (Mn) less than 20~0000 For polymers wlth ~n equal to or greater than 31 20,000, the preferred concentrations are in the range of 4 32 to 20 weight percent polymer, based on the total welght o~
33 the oil-polymer solution.

10~ ~'7~
l Oxid~tlon of thc oll-polymer ~olution 1~ conducted 2 for a time sufficient to lmpart to the solution a combined 3 oxygen content of about 0.01 to lO,O, eOg., 0.1 to 89 prefer-4 ably 0.1 to 5.0 weight percent, depending on the composition of the oil, the polymer and the concentration of polymer in 6 ~olution. Once the level of desired oxidation for a ~ven 7 oil and polymer has been determined at a given concentra~lon 8 of polymer in the oil, the color of ~he oxidized solution 9 may be later used as a standard for easily measuring the approxlmate degree of oxidation in subsequent batche~O
ll A more precise mea~ure of the degree of oxidatlon 12 is the specific absorption exhibited by oxygen containing 13 group functionality about 5.8 microns in the infrared. Oxy-14 gen group functionality may conveniently be measured w~th an infrared spectrometer using 0.05 mm to 0.5 mm specimen 16 thickness and sodium chloride cells. The oxygen group ab~
17 sorption in the useful range o~ oxidized solutions will 18 us;~ally be in the range of about 0.05 to 500 (based on a 19 0.5 mm cell) and depending on the oil9 polymer and polymer concentration. Usually, the lower absorption values can be 21 directly measured in a 0.5 mm cell, while higher absorption 22 values are best measured in thinner cells9 e.g.9 Ool mm or 23 .2 mm cells and the values may be extrapolated to a 005 mm 24 cell, if deslred for comparison purposes, as was done in some o~ the following examples. A~ used herein3 such terms ~6 ~ "oxidized", or "oxidized oil polymer solution" etc. in-27 dicates ~hat air or oxygen containing gas is used for the 28 oxidation, and precludes the use o~ other oxidative re-29 agents such as ozone.
Amine Compounds For Reaction With the Oxidized Oll-_olymer 31 Solution 32 Useful amine compound~ for condensation with the _ 20 -;9~
I. oxldized polymer-oll solu~ions to ~orm the polyam~nox prod-2 ucts o~ this inventlon lnclude amines of about 2 to 60, e.g , 3 3 to 20, total carbon atoms and about 1 to 12~ e.g.~ i to 6 4 nitrogen atom~ in th~ molecule, which amines may be hydro-carbyl aminea or may include other groups, e.g~9 1 ko 4 hy-6 droxy groups9 alkoxy groups, amide groups~ imidazollne groups 7 and the like.
8 Preferred amines are aliphatic, saturated amines~and include those o~ the general ~ormulae:
1l R-N-R" and R-N-(cH2)s-[-N-(cH2)s-]t~ R
12 R~ R' R' R' 13 wherein R, R' and R" are independently selected from the group 14 consisting o~ hydrogen; Cl to C12 straight or branched chain alkyl radicals; Cl to C12 alkoxy substituted C2 to C6 alkylene 16 radicals; C2 to C12 hydroxy or amino alkylene radicals, and 17 Cl to C12 alkylamino substituted. C2 to C6 alkylene radicals;
18 s is 2 to 6, preferably 2 to 4; and t is 0 to 10~ pre~erably 19 2 t~ 6.
Examples of suitable amine compounds represented by 21 the abuve include: n-octyl amine; n-dodecyl amine9 di-(2~
22 ethylhexyl) amine; 1~3-diaminoethane, 1~3~diaminopropane, 1,4-23 diaminobutane; 1,6-diaminohexane; diethylene triamine; tri-24 ethylene tetramine, tetraethylene penta-amine9 19 2~propylene diamine; di-(1,2-propylene) triamine; di (193-propylene) tri-26 amine; N,N-dimethyl-1,3-diaminopropane; N,N-di42-aminoethyl) 27 ethylene diamine; N,N~di-(Z-hydroxyethyl)-1,3 propylene diamine;
28 3-dodecyl oxy propylamine; N-dod.ecyl-193-propane diamine; di-29 ethanol amine; morpholine; tris-hydroxymethyl amino~ harle (THAM);
diisopropanol amine; etc.
31 Still other useful amlne compounds include: ali-32 cyclic diamines such a~ 1,4-di-(aminomethyl) cyclohexane and 33 heterocyclic nitrogen compounds such as imidaæolines and N-: - 21 ~

~,~6g8~

1 aminoalkyl piperazines of the general ~ormula:
2 CH2 ~ CH2 ~
3 NH2-(CH2)p - N N-G

wherein G is independently selected from th~ grvup consisting 6 of hydrogen and Q -aminoalkylene radicals o~ from 1 to 3 car-7 bon atomsj and p is an integer of from 1 to 4. Non-limiting 8 examples include 2-pentadecyl imidazoline; N~(2-aminoethyl) 9 piperazine; N (3-aminopropyl) piperazi~e, and N9NI-di(2-aminoethyl) piperazineO

11 Other alkylene amino compounds that can be used

12 include dialkylamino alkyl amine such as dimethylamino ethyl

13 amine, dimethylamino propyl amine, methylpropyl~mino amyl

14 amine, etc. These may be characterized by the ~ormula:
~ 2 176 H2N Rl ~ N

18 wherein Rl is an alkylene radical~ e.g~, an ethyleneJ pro-19 pylene, or butylene radical9 and R2 and R3 are Cl to C5 alkyl radicals.
21 Commercial mixtures of amine compounds may advan-22 tageously be used for the preparation o~ the polyaminox com-23 positions of this in~ention. For example9 one process for 24 preparing alkylene amines involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride) 26 with ammonia~ which results in a complex mixture of alkylene 27 amines wherein pairs o~ nitrogens are ~oined by alkylene 28 groups9 formlng such compounds as diethylene triamine, tri-29 ethylene tetra-amine, tetraethylene penta~amine and isomeric piperazlnes. Low cost poly(ethylene amines) compounds having 31 a composition approximating tetraethylene pentamine are ,~7arKs 32 available commercially under the trade ~ Polyamine H and ~ 1er ~c -~ral~ rl~
33 Polyamine 400 (PA-400). A similar mixture sold ~ Polyamine ~6ffj~ 87 8 1 500 (PA-500) is marketed by Jefferson Chem~cal C0~9 Mew Yor~, 2 N.Y. Similar materials may be made by the po~ymer~zation o~
3 aziridine, 2-methylazirldine and azetidine. I
4 The more important alk~lene polyamlne or allphatic polyamine compound, used in thls invention, can be broadly 6 characterized as an alkylene amino compound containing from 7 2 to 12 nitrogen atoms wherein pairs o~ nitrogen atoms are 8 ~oined by alkylene groups of ~rom 2 to 4 carbon atoms.
9 Condensation of Amine Compounds with Oxidized Polymer-Oil Solutions 11 Reaction o~ the amlne compound with the oxidized 12 polymer-oil solution takes place readily at a temperature ~n 13 the range of about 40C. to 300C., preferably a~ a tempera-14 ture in the range of 100Co to 200C. Accordinglyg after the oxidation of the oil polymer solution has reached the 16 desired level, the required amount of amine compound9 usu 17 ally in the range o~ about 0.1 to 4.0 WtG ~ based on the 18 weight of the polymer, may be added with m~ing and the 19 reaction mixture maintained at the required temperature while removing any water that forms. The time for completion o~
21 the reaction of the amine compound with the oxidized oil 22 polymer solution is in the order of about 15 minutes to ten 23 hours depending on temperature9 degree of mixing and re-24 activity of the amine compound. The final aminated product will usually contain in the range of about 0.03 ~o 59 e~gO
26 0.1 to 3.0 wt. % nitrogen, based on the total weight of the 27 aminated polymer-in-oil solution.
28 Use in Lubricating Oil , 29 The oil-soluble polya~lnox products of this inven-tion can be incorporated in lubricating oil compositions, 31 e.g., automotive or diesel crankcase lubricating oils9 in 32 concentratlons within the range of about 0.01 to 20 weight - 1 percent, e.g., 1.0 to 12 weight percent, pr~ferably 2.5 to 2 10.0 welght percent of the total composltlon. The lubr~cant~
3 to which the polyamlnox products o~ this lnventlon can be 4 added include not only hydrocarbon olls derived rrom petro-leum, but also include synthetic lubricants, polysilicone 6 oils, such as alk~l esters of dicarboxylic acids~ complex 7 esters, prepared by condensing either monohydric alcohols 8 or monocarboxylic acidJ with polyglycols an~ dicarboxylic 9 acids; alkyl esters o~ carbonic and phosphoric acids9 car~
boxylic acid esters of polyglycols9 etc.
11 Concentrates in oil of 5 to 70 wt. % polyamlnox 12 products may be used to facilitate handling. In the above 13 compositions or concentrates9 other conventional addltives 14 may be ~resent, including dyes9 pour point depressants9 anti wear agents~ antioxidants9 other viscoslty index improvers9 16 dispersants and the like. Such materlals include~ tricresyl 17 phosphate3 zinc dialkyl dithiophosphates having from 3 to 8 18 carbon atoms in the alkyl radlcalsg tert~octyl phenol sul~
19 fide; 4,4'-methylene bis (296~di~tert-butyl~pherol39 eth~
ylene propylene copolymers, polymethacrylates~ polyisobutyl-21 ene, etc.
22 This invention will be further unders~ood by ref-23 erence to the following Examples~ which include preferred 24 embodiments of the invention, and wherein all percents are weight percents.

27 Part A - 1250 gms. o~ an oil solution containing ; 28 7 percent by weight of Polymer A and 93 percent by weight 29 of Oil E are oxidlzed in a 2 liter flask at 170Co while vigorously agitating~ Air is introduced ln~o the solution 31 through a sintered glass ~parge until an lnfrared ~pec~ra 32 of a 0.5 mm thick sample shows that the absorptivity of the _ 24 -8~8 1 5.8 micron peak e~uals 0.40 The oxidation was then discon-2 tinued, and the oxidize~ oil-polymer ~olutlon wa6 removed 3 from the flask.
4 Part B - A small sample of the oxidized oil-poly-mer solution of Part A, was dialyzed by placing th0 ~am-ple 6 in a semi-permeable rubber membrane bag suspended in a Soxh-7 let extxactlon device where it was washed with condensing 8 hot hexane for about eight hours, in order to leach out the 9 oil fraction through the membrane into the hexane. At the end of this time, the hexane ~raction, which now contained 11 the low molecular weight oxidized oll fraction9 was placed 12 on a hot plate and blown with nitrogen to remove the hexane 13 solvent, leaving the oxidized (i.e., dialyzed) oil. Analysis 14 of thls dialyzed oil shows that it contains 0.25 percent by weight of oxygen. The polymer residue was washed out of the 16 dialysis bag inko a beaker with additional hexane9 which was 17 then evaporated off to leave the polymer residue. Analysis 18 of the residue showed it~contained 1.83 wt 4 ~ oxygenO
19 These anal~ses show that both the oil and the poly-mer become oxidized, although the polymer oxidized more~
21 which would be expected due to the presence of the unsatura 22 tion in the polymer resulting ~rom the ethylidene norbornene 23 component of the pol~mer.

A 20 gm. portion of the oxidized polymer~oil solu 26 t~on from Example 1, Part Agis condensed with 00125 gms.
27 of ethylene diamine. This reaction is carried ou~ in a 28 stirred, 50 cc. beaker at a temperature o~ 130C oJ whlle ~9 blowing nitrogen through the reaction mixture to remove the water that forms. The reaction is complete a~ter 1.5 hours 31 of such nitrogen stripping~ The reaction product contains 32 0.056 percent by weight of nitrogen.

_ ~ 25 -_ ~()6~7~

2 A 20 gm. portion of the oxidlzed polymer-oll solu-3 tion from Example 1, Part A, is condensed with 0.033 gms~ o~ -4 dlethylene triamine. The reaction conditions are described in Example 2~ This product is a clear and viscous fluid.
6 EXAMP~E 4 7 A 20 gm. portion of the oxidized solution from Ex-8 ample 1, Part A, is condensed with o.o48 gms. of ~riethylene 9 tetramine. The reaction conditions are the same as in Ex~
ample 20 This product is a clear and viscous fluid.

12 A solution of 232 gmsO of Polymer C and 543 gms.
13 o~ Oil E are oxidized in a well st~rred 2 liter glass re-14 actor at a temperature of 175C. Air is introduced through & sintered glass sparger in the bottom of the reactor at a 16 -r~te of 2200 cc/min. for 95 minutes. The resulting oxidized 17 solution has an infra-red (rR) 5.8 micron absorptivity of 18 o.80 in a 0.2 mm thick cell. The temperature of this oxi-19 dized intermed~ate is reduced to 155C. and 16 gm9 o~ Poly amine H are added. This mixture ~s maintained at about 155C.
21 while stirred and blown with nitrogen for three hoursO The 22 final product is a clear, brown fluid with a kinematic vis-23 cosity of 549 centistokes at 210F. and a nitrogen content 24 of o.63 percent by weight.

26 A solution of 236 gms. of Polymer B and 550 gms.
27 of Oil E is oxidized at 183C. using an air rate of 2200 28 cc/min.~ while stirringO After 97 minutes the oxidized solu-29 tlon has a 508 micron absorpti~ity (I~) of 0.90 (0.2 mm cell).
This solution is cooled to 155C., 16 gms. of Polyamine H
31 are added and the mixture is stripped with nitrogen for 3 32 hours. The ~lnal product is a clear fluid with a kinematic . ~ .

'7~3 1 visco~ity of 182 centistoke~ at 210F., an~ a nltrogen con-2 tent of o.63 percent by weight.
3 EXAMPLE_7 4 670 gms. of a solution containing 30 percent by weight o~ Polymer D and 70 percent by weight of 011 ~ are 6 oxidized in a well stirred, 2 liter, glass reactor at a tem-7 perature of 182C. Air is introduced at a rate of 2200 cc/
8 min. for 90 minutes. The oxidized solution has a 5.8 micron 9 peak absorptlvity of o.76 (0.2 mm cell), The temperature is reduced to 155C. and 14 gms. of Polyamine H are added. This 11 mixture is then stirred and blown with nitrogen for three 12 hours9 while at about 155C. The final product is a clear 13 fluid with a kinematic v~scosity of 147 centistokes at 210F~
14 and a nitrogen content of o.64 percent by weight.
~AMPLE 8 16 A 875 gm. solution containing 30 percent by weight 17 of Polymer E and 70 percent by weight of Oil E is oxldized 18 at a temperature o~ 170C. using an air rate of 2200 cc/
19 minute while stirring. The 5.8 micron absorptivity is o.80 (.2 mm cell) after 135 minutes of oxidation. This solution 21 is cooled to 150C. and 18 grams of Polyamine H are addedO
22 The mixture is then stripped with nitrogen ~or 2 hours while 23 at 150C. The final product is a clear ~luid with a kinemàtic 24 viscosity of 1183 centistokes at 210F. and a n~trogen content 0.73 percent by weight.

-27 A solution composed of 60 gms. of Polymer F and 28 140 gms. of Oil E is oxidized in a 500 ml. round bottom flask 29 at a temperakure of 165C. to 169C.9 whlle stirrlng. Air is in~ected into this well agitated solution at a rate of 31 240 cc/min. and af'ter 45 minutes the 5.8 micron peak ab-32 sorptivity is 0.42, (0.2 mm cell). Thls oxldized solution ~ tr~e rt~ 27 -~ - .

'7~3 1 is cooled to 160C. and 1 percent by wei~ht, ba~ed on the 2 wèight of the oxldized solutlon, of tetraethylene penta-3 amine (TEPA) is added. The mix-ture is stripped w~th nitrogen for 2 hours at a temperature o~ 150~C. The final produc~
is a clear viscous fluid~
6 EXAMPLE_10 7 A solution composed of 100 gms. of Polymer G and 8 100 gms. of Oil E is ox~dized with alr at a temperature of 9 165CoJ while stirringO The air is introduced at a rate of 520 cc/min. and after 90 minutes the solution has a 5.8 mic-11 ron peak absorptivity of 1.0 (0.2 mm cell).

13 A 100 gm. portion of the oxidized solution ~rom 14 Example 10 is mixed with 2.8 gms. of TEPA and is stripped with nitrogen ~or 2 hours at 160C. The final product is a 16 viscous clear fluid.

18 A 100 gm. portion o~ the oxidlzed solution from 19 Example 10 is mixed wi~h 4 gms. of N,Ndime~hyl 1-3 propane diamine. This mixture is condensed in a 500 ml. round bottom 21 reaction flask equipped with a water vapor condenser ~or 2 22 hours at a temperature of 120C. This solution is then strip-23 ped with nitrogen for 2 hours at 160C.
2~ EXAMPLE 13 100 gmsO of Polymer H are dissolved in 100 gms. of ~6 Oil E and the solution is oxidized with air at a temperature 27 of 165C. while stirring. Air is in~ected at a rate of 240 28 cc/min. and after 140 minutes the oxidized solution has a 29 5.8 micron absorptivity of' 0.88 (0~2 mm cell) ~ A 100 gm.
portion o~ thls oxidized solution is m~xed with 1.5 gms. of 31 TEPA and stripped with nitrogen blowing f'or two hours while 32 at 160C. The final product 1~ a c~ear flu:Ld.
:;
- ~ 28 '7~
-1 EXAMPL~ 14 .
2 An oil solution composed of 66 gms. o~ Polymer I
3 and 134 gms. of Oil E is oxldized with air atla temperature 4 of 170C. The air is in~ected at a rate of 420 cc/min. into solution ~or 130 minutesg while stirring~ untll the peak at 6 5.8 micron has an absorbtivity of 0.81 (0.2 mm cell)O This 7 oxidized oil solution is condensed with 2 percent b~ weight9 8 based on the weight of the oxidized oil solution, o~ tetra-9 ethylene-pentamine by stripp~ng with nitrogen ~or three hours at a temperature of 150C.

12 An oil solution composed of 66 gms. of Polymer J
12 and 134 gms. of Oil E is oxidized with air at a temperature 13 of 170C. The air is injected at a rate of 420 cc/min. into 14 the stirred solution through a slntered glass sparger~ A~ter 90 minutes this oxidized solution ha,s a 5.8 micron peak ab-16 sorptivity of 0.88 (092 mm cell). This oxidized oil æolu-17 tion is condensed with 2 percent by weight of tetraethylene-18 pentamine for three hours at a temperature of 150C. while 19 nitrogen blowing.
d Inhibi~ion Bench SIB~ Test for Dispersancy 21 ~he dispersant activity of the polyaminox products 22 of the preceding Examples ~a5 determined in a SIB (Sludge 23 Inhibition Bench)' ~est as follows:
24 A usedJdispersant-free, automotive mineral lubri~
cating oil, containing a viscosity index (V.I~) improver9 a 26 pour point depressantJ and a zinc dialkyldithlophosphate 27 anti-wear agenk, which oil had an original viscoslty o~ 325 28 SUS at 100F. was obtained by pooling the oi~ drained from 29 the crankc~es of a fleet of taxicabs operating in New York City. The used oil i5 centr~,.fu~,ccl ln heavy-walled 50 ml.
31 tubes at about 16,000 RPM ~or one~half hour and the clear~

~ 8'-~
1 supernatant oil, whlch is ~ree of ~ludge but contains dis-2 solved thereln ~ludge precursors, is decanted ~rom the sludge 3 and used in the SIB Test.
4 In conductlng the test either 0.4 or 005 wt. ~ of the above polyaminox products was dissolved lnto the used, 6 centrifuged oil and added to preweighed centr~fuge t,ubes.
7 The tubes were stored in a heating block at 280~F. (138~C) 8 for 16 hoursJ along with tubes contain~ng blanks9 l~eO, con-9 taining only the centri~uged used oll to which no dlspersant additive was added. After heating for 16 ~ours9 the tubes 11 are centrifuged at 169000 RPM for one half hour ~nd the super~
12 natant oil decanted and discarded. The tubes are ~nverted 13 and allowed to drain in a rack for not more than 15 minutesp 14 after which the walls o~ each tube aré rinsed with 25 mlO of n-pentane, taking care not to disturb the sludg~ compacted in 16 the tip of each tube. A second 25 ml. portion o~ pentane 17 is added to each tube and the sludge dispersed and any oc-18 cluded oil dissolved by gentle sha~ing. ~he tubes are now 19 centrifuged in an explosion-proof9 refrigerated centri~uge at 16,000 RPM for one-half hour, the pentane decanted and 21 discarded. A~ter r~nsing the exterior of each ~ube with 22 acetone, the tubes and contents are allowed to dry at room 23 temperature for one hour and weighed9 the weight of sludge 24 in each tube being obtained by di~ferenceO The e~fective~
ness of the dispersant is expressed as the weight of sludge 26 ~ound in each tube containing dispersantD as compared to the 27 weight of sludge ~ound in the blanks, which had no dispersant.
28 Thus, 100% would indicate no dispersancy~ with lower percent- -29 ages showing dispersancy.
For comparison, the above test was run using 0.4 31 wt. % o~ two lubricating oil di~persants repre~entatlve Or 32 commercial dispersants now in widespread use. Compar~son - 30 ~

37~3 1 Dispersant-A (CD-A) was a 50 wt. ~ concen~rate in oil o~ the 2 imide condensation product of about 1.3 molar propor.~ion o~
3 polyisobutenyl succinic anhydrlde with a molar proportion of .,~, ~ .
,` 4 Polyamine H. Comparison Dispersant B (CD-B) was a 50 wt. %
concentrate in oil of the imide condensation product o~ about 6 2.8 molar proportions of polyisobutenyl succinic anhydride 7 with a molar proportion o~ Polyamine H. The polyisobutenyl 8 ~roup of said two comparison dispersants had a molecular 9 weight of about 1000.
The compositions tested and the results obtained 11 are summarized in Table III, which ~ollows:

~r.~de ~arK

- 31 ~

8t78 2 DISPERSANCY IN S.I.B. TEST OF OXIDIZED OIL-3 _ POLYMER SOLUTIONS REACTED WITH AMI~E
4 Dlspersancy,~
Ex. Wt ~ Dispersant % Nitrogeno~ Blank 6 2 O, 5 .os6 55 7 3 o . 5 _ L~7 8 4 0~5 - 39 9 5 0.4 .63 16 6 0.4 .63 ~ 25 11 7 -4 .64 35 :
12 8 0.4 .73 14 13 9 0.4 _ 25 14 11 0.4 - 6 - ~ .
12 ~4 ~ 55 16 13 0~4 - 65 :
17 14 0.4 - 73 . ;. ~ .
18 15 0.4 - 66 19 CD-A 0.4 - 40 ~ .
CD-B 0~4 1.14 80 21 As seen by Table III, the various produc~s of the 22 invention, i,e., the products of Examples 2 to 9, and 11 to 23 15 all showed dispersancy in the test. Many of the inven-24 ti~e products, even though of a low nitrogen concentration, ;~
were very effective. To illustrate, 0.4 wt~ ~ of the prod-26 uct of Exampie 6, analyzed o.64 wt. % ~itrogen, and was more 27 effectlve than 0.4 wt. ~ o~ the comparlson dispersant CD-B, 28 whlch analyzed 1.14 wt. % nitrogen.

~ ~6 1 ~XAMPLES 1~ to ~0 2 In a manner simil~r to that prevlously described 3 a series of oxidations were carried out b~ blowing air 4 through various heated solutions o~ polymer in oil9 whlle rapidly stirring.
6 of these oxidations, Examples 55~ 59 and 60 were 7 pilot plant batches. Examples 55 and 59 were carried out 8 in a 300 gal. reactor, which Was stirred at 100 rpm. Air 9 was blown through the polymer-in-oil solution at 360 SCFH
(standard cubic feet per hour). Example 60 was carried out 11 ~n a 50 gal. reactor9 stirred at 350 rpm, and blown with an 12 air rate of 60 SCFH. All of the other examples were labora-13 tory batches, and the oxidations were carried out using air 14 at the rate of about 1000 cc. per minuteJ except for Example 299 where the air rate was about 240 cc~ per m~nute. Stirring 16 in the laboratory examples was by a high speed propeller 17 laboratory mixer operating at about 2000 rpm. ln the case 18 of Examples 16 to 299 while the remainder of the labor~tory 19 examples were stirred at about 1500 rpm~ The polymers and oils used in these examples are those previously identified 21 in Tables XI and I9 respectively.
22 Table IV9 which follows9 summarizes the polymers 23 and OilS used9 the pertinent conditions for the oxidat~on9 24 the absorptivity at the 5.8 micron level at the end of the oxidation9 and the thickening e~iciency (T~E.) o~ the poly-26 mer initially9 and after oxidation~ The absorptivity is 27 based on a 0.5 mm thick9 NaCl cell. Usually9 for absorp~
28 tivity values of less than 1, the absorptivity value was d~-29 rectly determined in a 0.5 mm cell. For values greater than 1~ then usually a thinner cell, generally a 0.05 mm cell, was 31 used9 and the readings were then extrapolated to a value ~or 32 a 0.5mm. ce~ inorder to place all the absor~tivlties on the same .
- 33 ~

- ~. .. .. ..

;'8 basis for comparison. The lnltial thickening e:~iciency was 2 determined by the vlscosity increase upon ~lssolvlng the 3 polymer in the oil. The ~lnal thickening ef~lclency was 4 determined by measuring the viscosity of the oxidized poly-mer-in-oil solution and ascribing all the viscosity change 6 to the oxidation breakdown Or the polymer on the bas~s that 7 any change in the viscoslty of the oil per se due to oxida~
8 tion was negligible.

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~o ~urther 111u~trate rrable IV, khe tab~e will be 2 followed through with regard to Example 16. Here, the 3 char~;e to the reactor wae 1400 grams . The charge corlsl s ted 4 of 7 wt . r~ of Polymer A ( def ined ln the preceding Table II) 5 dissolved in 93 wt. % of Oil E (de~ined in Table I). The 6 vlscosity of the polymer-in-oil solution ~howed Polymer A
7 had an initial thickening efficiency (T.E.) of 3Ø 1400 8 grams o~ the polymer-in-oil solution was heated to about 9 340F. in the reaction flask, and air was blown through the 10 charge f`or one hour, ~ollowed by cooling to room temperature.
11 ~he 5.8 micron I~-R- absorption o~ the oxidized product, using 12 ~ 0.5 mm. cell, was o,480. The viscos~ty of the oxidized 13 polymer-in-oil solution showed the oxidized polymer ha~ a 14 final thickening eff ic iency of l .47 .
The preceding oxidized polymer-in-oil solutions o~
16 Examples 52 and 55 were sepaxated into the oxidized polymer 17 and the oxidized oil fractions, by di&lysis through a semi-18 permeable membrane in a manner similar to that prev?ously 19 described. The two resulting fractions were than analyzed for oxygen content. For Exa~ple 52, the oxidized polymer 21 contained 1.26 wt. ~ oxygen, while the oxidized oil contain-22 ed ~39 wt. r~ oxygen. For Example 55, the oxidized polymer 23 contained 0.411 wt. % oxygen, while the oxidized oil con 24 tained o.266 wt. 5~ oxygenO
EXAMPLES 61 to 96 26 Various of the oxidized polymer-in~oil solutions 27 o~ Examples 16 to 60, or of the same type, bu~ of a di~erent A~ 28 batch, were aminated by reaction with Polyamlne 400 (PA-400) 29 with nitrogen blowing to remove any water ~ormed~ and then - 30 tested at a 1 wt. ~ concentration ~or di~per~ancy in the pre-31 viously described S.I.B.r~st; the data belng shown in Table V.
~r~e n~rl~

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-- 41 - .
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To further illu~trate Table V" consider E:xample 61.
2 Here, 10 grams o~ the Oxldized Solution of Example 16 was 3 aminated, i.e., reacted, with 0.19 wt. ~ based on the weight 4 of oxidized polymer~ln~oil solutiong o~ Polyamine 400~ i.e., 0.19 grams of Polyamine 400. The reaction was carr~ed out 6 by heating the mixture at 130~. for 2 hours~ while blowing 7 with nitrogen to remove any water that forms~ The product 8 was then cooled to room temperature, and a portion o~ the 9 resulting aminated productg w~thout any further puriflcation~
was then tested in the SoI~B~ Test9 at a concentration of 1 11 Wt. ~9 i.e~9 0.1 gram of the aminated product per 10.0 12 grams of ~he used oll. In Example 61~ the S.I9B. Tes~ gave 13 ~ reading o~ 33~ o~ the blanka thus indicating good disper-14 sancyO
To further illustrate9 consider Example 750 Here, 16 the Oxidized Solution that was used was a 1~ (type) meaning 17 that it had been prepared in the same manner as the afore~
18 described Example 169 but was a di~ferent batch -19 EXAMPLES 97 to ~12 Examples 97 to 112 were prepared in the general 21 manner described wlth re~ard to Examples 61 to 96 by simply 22 heating the oxidized polymer in oil solution with the amine 23 while blowing nitrogen 'chrough the reaction mixture to re-24 move water or other volatile~O
Since it had been found that free amine will pre-26 cipitate zinc C4~5 dialkyl dithiophosphate from an oil solu-27 kion9 a te~t w~ devised to en~ure the completion cf the 28 a~oresaid amination reaction. The test (Zin~c~ Precipitation 29 Test) was carried out by mak~ng up a mixture of 10 wt. ~ of the reaction mixture o~ the amine and ~he oxidlzed polymer-31 in-oil~ 1 wt. ~ of an oil concentrate containlng about 25 32 wt. ~ of a light mineral oil and dl~olved therein, about ~r~de ~r ,K - 4 2 1 75 Wt. % of a ZinC dl~lkyl dithlopho5phate prepared by re-2 acting a mixture of' about 65 w t . ~ isobutyl alcohol and a~out 3 35 wt. ~ o~ mixed primary amyl alcohols with PzS5 and then 4 neutrallzing with zinc oxide, and about 89 wt, ~ of a white mineral oll. After 4 20 hours heating at 180F.9 ~ there is 6 unreacted, i.e., free, amine present~ then a visually ob-7 servable haze will form due to precipitation of the zinc 8 dialkyl dithlophosphate, thus indicating that ~urther heat- -9 ing is necessary to complete the reaction.
Completion o~ the amination reaction had occurred 11 in all cases of Examples 97 to 112, as determined by the 12 aforesaid Zinc Precipitation Test. In some casesg where the 13 initial Zinc Preclpitation Test had shown the reaction was 14 not completed, then the temperature was generally raised and heating was continued for several more hours in order to com-16 plete the reaction.
17 The conditions ~or preparing these examples are 18 summarized in Table VI which ~ollows.

_ 43 _ .

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C) U~ O O C~ 0 00 00 0000 0 0 ~r) ~) ~ ~ ~ ~r)0 ~)00 ~0 tr)oo ~t J' E~

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~ o~
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- 45 ~

~ 7 8 1 A~ ~een by Table VI9 variou~ amines w~re reacted 2 with the oxldized polymers by slmple heating wi~h nitxogen 3 blowing~ Some of~ ~he Example~ were heated in two stages9 4 such as Example 106, where 8000 grams o~ an oxidized polymer-in-oil solution of an Example 16 type9 i.eO9 oxidized ac 6 cording to Example 16 but a di.'ferent batch9 which had been 7 oxidized to a 0~176 absorptivlty9 was reacted with 0~4 wt~%
8 (iOe., 32 grams) of diethanolamine for 2.5 hours at 130C.
9 followed by heating at 180Co for another 2 hours.

~ 46 ' 1 Engine Test Examples: 10~98 78 2 Part A - A ~ully formulated lOW-30 SAE crankcase 3 lubricatlng oil containing a zinc dialkyl dithiophosphate 4 for anti-wear and e.p~, an ethylene-propylene copolymer as a V.I. improver, a detergent-inhibitor package, anti-6 rust, and a commercial polyisobutylene-succinlc anhydride-polyamlne type dispersant CD-A (previously described), was 8 tested in a MS~Sequence V C engine test. For comparison, 9 the same formulation was tested~ but in place o~ the above dispersant, the dispersants of Examples 94 and 96 were used 11 ~nstead, ~t an even lower concentration.

12 The Sequence V-C engine test is definltively de~

13 scribed in "Multicylinder Test Sequence for Evaluating Auto~

14~ motive Engine Oils.'l ASTM Special Technical Publieation 315F, page 133 ~f (1973). The V-C test evaluates the ability 16 of an oil to keep sludge in suspension and to keep varnish 17 deposits from pistons, valves and other engine parts.

18The test results are shc~n below in Table VII.

- 21OF THE I~ENTION AGAINST CONVENTIONAL DISP RSANT

22_ MS-VC Test Results 23 Wt.% N-24containing Skirt Total Dispersant Polymer Sludge Varnish Varnish 26 Example 94 1.2 - 8.o 7.7 8.o 27 Example 96 1. 8 8 . 7 8 . o 8 . 2 28 CD-A 2.1 7.3 7.8 7,4 29As seen by Table VII the fully formulated crankcase oil containing 2.1 wt. ~., on an active ingredient basis~ Or 31 the commercial polyisobutenyl succinimide gave a sludge 32 rating of 7.3, a piston skirt varnish rat~ng o~ 7.8 and a 33 total varnish rating of 7.4. All of these ratlngs are on a . .

:
.
.. . .

1 basis Or O -to 10, wher~ O ls very poor, and 10 is completely 2 clean. In comparison, by substitutin~ the pro~uct o~ Ex~mple 3 94, in an amount sufflcient to give 1.~ w~ of the amina 4 ted polymer, ~or the 2.1 wt. % of said succin~mide disper-santJ better sludge and to~al varnish results were obtained, 6 while the piston skirt varnish was abouk the same. Using 7 sufficient of the product of Example 96 to give about 1.8 8 wt. % aminated polymerJ in place o~ the 2.9 wt. ~ succin-9 imide gave better results than the succinimide. ThusJ the engine date of Table VII shows that-products o~ the inven~
11 tion are ~ffective in keeping the engine clean.
12 Part B - Another series of MS-VC engine tests were 13 carried out on sald fully ~ormulated lOW-30 SAE crankcase 14 lubricant containing the zinc dialkyl dithiophosphateg eth-ylene-propylene copolymer as V.Ii improver, the CDWA ashless 16 dispersant, a detergent-inhibitor package and an anti rust 17 agent. In this series, various of the high molecular welght 18 aminated products o~ the invention~ which were also effective ~
19 as V.I. improvers, were substituted for the ethylene~propylene -in order to demonstrate the added improvement in cleanliness 21 obtai~ed when the V~I. improver polymer is aminated in ac-22 cord with the invention. As a fur~her comparison9 a commer~
23 cially available nitrogen containing acrylate type polymer ;/ ~f 24 (Acryloid 954) was substltuted for the ethylene propylene copolymer. In each of the casesJ the amount of the aminated 26 products of the invention~ or the amount of the Acryloid 954 27 that was used, was su~f icient to give the same thickening 28 e~fect as the ethylene-propylene copolymer that it was re-29 plac ing ~
The results of the tests of Part B are summarized Vlll 31 in Table ~t~ which follows.

tr~e rn~r~
- 1~8 -8'~
1 TAsLE VIII
2 MS-VC ENGIN~ TEST COMPARING V.I. IMPROVERS OF THE
3 INVENTION AGAINST CONVE~rIONAL V.~. ~MPROVERS
4 MS-VC Test Results Wt.~ N- Plskon 6 containing Skirt Total 7 V.I. Improver Polymer Sludge Varnish Varnish __ 8 Ethylene/pro-.54 8.35 8.2 7D7 9 pylene copoly-mer 11 Example 112 .56 9-3 8.7 8.9 12 Example 98 .66 8.8 8.3 8.8 13 Example 99 ~73 9- 8.3 8-3 14 Example 74 ,57 8.~ 8.4 8.0 Example 95 .60 9.0 8.6 802 16 Example 100 .66 8.9 8.2 8~9 17 Example 101 .80 9.1 803 8.6 18 Acryloid 9541.64 8.6 8~6 8.0 19 Table VIITillustrates the effect of aminating the ethylene-propylene terpolymers (Examples 1129 989 99~ 74y 21 95, 100, 101) in improving the cleanliness of the englne 22 as compared to a non-aminated ethylene=propylene copoly~ :.
23 mer. A1SOJ smaller amounts of the aminated polymers of 24 these Examples of the invention gave engine results com parable to the commercial Acryloid VI-dispersan~ material 26 in this formulation.

~t~Ae m~

_ 49 _ . .
.- . . . .

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of an oil soluble, sludge dispersing, aminated oxidized mineral lubricating oil solution of an ethylene copolymer having a number average molecular weight (?n) in the range of about 500 to 500,000, which comprises first air oxidizing, wherein air is the sole oxidizing agent, a mineral lubricating oil solution containing about 4 to 60 wt. %, based on the weight of the oil solution, of said copolymer dissolved in a mineral lubricating oil having a viscosity in the range of about 50 to 1000 SUS at 100°F., said copolymer comprising 30 to 80 wt.% ethylene, about 70 to 20 wt. % of a higher C3 to C18 alpha olefin, and about 0 to 15 wt. % of a C5-12 non-conjugated diolefin; at a temperature of 80°C. to 300°C. to form an oxidized oil solution containing in the range of about 0.01 to 10.0 wt. % oxygen, based on the weight of said oil solution, and then secondly, aminating said oxidized oil solution with about 0.1 to 4.0 wt. %, based on the weight of said polymer, of an amine of 2 to 60 total carbon atoms having 1 to 12 nitrogens, wherein said amine is selected from the group consisting of hydroxy amine having 1 to 4 hy-droxy groups and polyamines having the general formulae:

and wherein R and R' are independently selected from the group consisting of hydrogen, C1 to C12 straight or branched chain alkyl radicals, C1 to C12 alkoxy C2 to C6 alkylene radicals, C2 to C12 hydroxyalkylene radicals, C2 to C12 aminoalkylene radicals and C1 to C12 alkylamino C2 to C6 alkylene radicals;

G is independently selected from the group consisting of hy-drogen and .OMEGA. -amino-alkylene radicals of from 1 to 3 carbon atoms; s is a cardinal number of from 2 to 6; t is a cardinal number of from 0 to 10; and p is an integer of from 1 to 4;
and wherein said aminating gives a final product having in the range of about 0.03 to 5 wt. % nitrogen, based on the total weight of the aminated oxidized oil solution of polymer.

2. A process according to claim 1, wherein the number average molecular weight (?n) of said copolymer is in the range of 1500 to 80,000, the ratio of the weight average molecular weight (?w) to the number average molecular weight (?w/?n) of said copolymer is less than 10, said copolymer has a crystalline content of less than 25 percent by weight, said oxidized oil solution contains in the range of about 0.1 to 8 wt. % oxygen, said amine is a polyamine, and said final product contains about 0.1 to 3.0 wt. % nitrogen.

3. A process according to claims 1 or 2, wherein said copolymer is a copolymer consisting of ethylene and pro-pylene, and said amine is a polyethyleneamine.

4. A process according to claims 1 or 2, wherein said copolymer is a terpolymer of 30 to 80 wt. % ethylene, 70 to 20 wt. % propylene and 3 to 10 wt. % non-conjugated di-olefin, and said amine is a polyethyleneamine.

5. A process according to claim 1 where said non-conjugated diolefin is selected from the group consisting of 1,4-hexadiene; 5-methylene bicyclo (2,2,1) 2-heptene; 5-ethylidene bicyclo (2,2,1) 2 heptene; and dicyclopentadiene.

6. A composition which is an oil soluble, sludge dispersing, aminated oxidized mineral lubricating oil solution of an ethylene copolymer having a number average molecular weight (?n) in the range of about 500 to 500,000, which has been prepared by: first oxidizing with air as the sole oxi-dizing agent, a mineral lubricating oil solution containing about 4 to 60 wt. %, based on the weight of the oil solution, of said copolymer dissolved in a mineral lubricating oil having a viscosity in the range of about 50 to 1000 SUS at 100°F, said copolymer comprising 30 to 80 wt. % ethylene, about 70 to 20 wt. % of a higher C3 to C18 alpha olefin, and about 0 to 15 wt. % of a C5-12 non-conjugated diolefin; at a tempera-ture of 80°C. to 300°C. to form an oxidized oil solution con-taining in the range of about 0.01 to 10.0 wt. % oxygen, based on the weight of said oil solution, and then secondly, aminat-ing said oxidized oil solution with about 0.1 to 4.0 wt. %, based on the weight of said polymer, of an amine of 2 to 60 total carbon atoms having 1 to 12 nitrogens, wherein said amine is selected from the group consisting of hydroxy amine having 1 to 4 hydroxy groups and polyamines having the general formulae:

and wherein R and R' are independently selected from the group consisting of hydrogen, C1 to C12 straight or branched chain alkyl radicals, C1 to C12 alkoxy C2 to C6 alkylene radicals, C2 to C12 hydroxyalkylene radicals, C2 to C12 aminoalkylene radicals and C1 to C12 alkylamino C2 to C6 alkylene radicals;

G is independently selected from the group consisting of hydrogen and .OMEGA. -amino-alkylene radicals of from 1 to 3 carbon atoms; s is a cardinal number of from 2 to 6; t is a cardinal number of from 0 to 10; and p is an integer of from 1 to 4;
and wherein said aminating gives a final product having in the range of about 0.03 to 5 wt. % nitrogen, based on the total weight of the aminated oxidized oil solution of polymer.

7. A composition according to claim 6, wherein the number average molecular weight (?n) of said copolymer is in the range of 1500 to 80,000, the ratio of the weight average molecular weîght (?w) to the number average molecular weight (?w/?n) of said copolymer is less than 10, said co-polymer has a crystalline content of less than 25 percent by weight, said oxidized oil solution contains in the range of about 0.1 to 8 wt. % oxygen, said amine is a polyamine, and said final product contains about 0.1 to 300 wt. % of nitrogen.

8. A composition according to claims 6 or 7, wherein said copolymer is a copolymer of 60 to 80 wt. % ethylene and the remainder propylene, and said amine is a polyethyleneamine.

9. A composition according to claims 6 or 7, wherein said copolymer is a terpolymer of 30 to 80 wt. % ethylene, 70 to 20 wt. % propylene and 3 to 10 wt. % diolefin, and said amine is a polyethyleneamine.

10. A composition according to claim 4, wherein said non-conjugated diolefin is selected from the group con-sisting of 1,4-hexadiene; 5-methylene bicyclo (2,2,1) 2-heptene; 5-ethylidene bicyclo (2,2,1) 2-heptene; and di-cyclopentadiene.

11. A lubricating composition comprising a major amount of a lubricating oil and about 1 to 12 wt. % of a sludge dispersant which is an oil soluble, sludge dispersing, aminated oxidized mineral lubricating oil solution of an ethylene copolymer having a number average molecular weight (?n) in the range of about 500 to 500,000 which has been prepared by: first air oxidizing with air as the sole oxidizing agent, a mineral lubricating oil solution containing about 4 to 60 wt. %, based on the weight of the oil solution, of said copolymer dissolved in a mineral lubricating oil having a viscosity in the range of about 50 to 1000 SUS at 100°F., said copolymer comprising 30 to 80 wt. % ethylene, about 70 to 20 wt. % of a higher C3 to C18 alpha olefin, and about 0 to 15 wt. % of a C5-12 non-conjugated diolefin; at a temperature of 80°C. to 300°C. to form an oxidized oil solution containing in the range of about 0.01 to 10 0 wt. % oxygen, based on the weight of said oil solution, and then secondly, aminating said oxidized oil solution with about 0.1 to 4.0 wt. % based on the weight of said polymer, of an amine of 2 to 60 total carbon atoms having 1 to 12 nitrogens, wherein said amine is selected from the group consisting of hydroxy amines having 1 to 4 hydroxy groups and polyamines having the general formulae:

and wherein R and R' are independently selected from the group consisting of hydrogen, C1 to C12 straight or branched chain alkyl radicals, C1 to C12 alkoxy C2 to C6 alkylene radicals, C2 to C12 hydroxyalkylene radicals, C2 to C12 aminoalkylene radicals and C1 to C12 alkylamino C2 to C6 alkylene radicals;
G is independently selected from the group consisting of hydrogen and .OMEGA. -amino-alkylene radicals of from 1 to 3 carbon atoms; s is a cardinal number of from 2 to 6, t is a cardinal number of from 0 to 10; and p is an integer of from 1 to 4; and wherein said aminating gives said sludge dispersant, which has in the range of about 0.03 to 5 wt. % nitrogen, based on the total weight of the aminated oxidized oil solution of polymer.

12. A lubricating composition according to claim 11, wherein the number average molecular weight (?n) of said copolymer is in the range of 1500 to 80,000, the ratio of the weight average molecular weight (?w) to the number average molecular weight (?w/?n) of said copolymer is less than 10, said copolymer has a crystalline content of less than 25 percent by weight, said oxidized solution contains in the range of about 0.1 to 8 wt. % oxygen, said amine is a polyamine, and said sludge dispersant contains about 0.1 to 3.0 wt. % nitrogen.

13. A composition according to claims 11 or 12, wherein said copolymer consists of ethylene and propylene, and said amine is a polyethyleneamine.

14. A composition according to claims 11 or 12, wherein said copolymer is a terpolymer of 30 to 80 wt. % ethylene, 70 to 20 wt. % propylene and 3 to 10 wt. % diolefin, and said amine is a polyethyleneamine.

15. A composition according to claim 11 wherein said non-conjugated diolefin is selected from the group consisting of 1,4-hexadiene; 5-methylene bicyclo (2,2,1) 2-heptene; 5-ethylidene bicyclo (2,2,1) 2-heptene; and dicyclo-pentadiene.