CA1279318C

CA1279318C - Hydrocarbon compositions containing polyolefin graft polymers

Info

Publication number: CA1279318C
Application number: CA000504852A
Authority: CA
Inventors: Christopher Soudang Liu; Maria Magdalena Kapuscinski; William Pius Hart; Larry Dale Grina
Original assignee: Texaco Development Corp
Current assignee: Afton Chemical Additives Corp
Priority date: 1985-04-29
Filing date: 1986-03-24
Publication date: 1991-01-22
Anticipated expiration: 2008-01-22
Also published as: JPS61250013A; EP0201164A2; DE3686835D1; BR8601879A; DE3686835T2; EP0201164A3; EP0201164B1; US4640788A; AU5636286A; AU585339B2

Abstract

HYDROCARBON COMPOSITIONS CONTAINING
POLYOLEFIN GRAFT POLYMERS

ABSTRACT OF THE DISCLOSURE

Lubricants of improved properties contain ethylene-propylene copolymers bearing graft units derived from, as a functional monomer, the reaction product of (i) an unsaturated aldehyde or ketone and (ii) a primary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring.

Description

~2~3~
HYDROCA~BON COMPOSITIONS CONTAINING

.
(D#7a,411-F) . FIELD OF THE INVENTION
This invention relates to hydrocarbons including hydrocarbon lubricating 0119. More pa~tic~larly, it relates to hydrocarbons which contain gra~t polymers which permit attainment of improved prGperties.

BACRGROUND OF THE INVENTION
As is well known to ~hose skilled in the art, hydrocarbon fuel~ and lubricating oils must be ormulated, as by addi~ion of various additives, to improve their properties.

In the case of lubricating oils, typified by tho~ employed in railway, automotivc, aircraft, marine, etc.
s~rvice, it i9 ~ound that they become degraded during use due inter alia to ~ormation of sludgQ which may be generated by d~terioration o~ the oil or by introduction of undesirable component3 from othar sources including the ~uel or the combu~tion air. In order o maintain and improve the properties of the lu~ricating oil, various additives have heretofore been provided; and these have been intended to improve the viscosity index, dispersancy, oxidative stability, etc. It is an object of thi~ invention to provide an additive system which permits attainmen~ of improved hydxocarbons.
Other ob~ects will be apparent to those skillad in ~he ar~.

~2~93~

STATE~ENT OF THE INVENTION
In accordance with certain of its aspects, this invention is directed to a graft polymer comprising an oil-soluble, substan-tially linear, carbon-carbon backbone polymer having graft polymer~
ized thereon functional units derived from the reaction product of (i) an ethylenically unsaturated aldehyde or ketone and (ii) a pri-mary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring.
According to another aspect of the present invention there 10 i5 provided the process for preparing a graft polymer which comprises intimately admixing in a reaction mixture (i) an oil-soluble, sub-stantially linear, carbon-carbon backbone polymer, (ii), as a fun-ctional monomer, the reaction product of (i) an unsaturated aldehyde or ketone and (ii) a primary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring, and (iii) a free radical initiator; maintaining the temperature of the reaction mix-ture at a temperature at least as high as the decomposition tem-perature of said initiator thereby effecting decomposition of said initiator and graft polymerization of said functional monomer onto said backbone polymer to form graft pol.ymer; and recovering said graft polymer.
DESCRIPTION OF THE INVENTION
The charge polymer which may be employed in practice of the process of this invention may include an oil-soluble, substan-tially linear, carbon-carbon backbone polymer. Typical carbon-carbon backbone polymers prepared from monomers bearing an ethyleni-cally unsaturated polymerizable double bond which may be employed `` 1~7~3~8 - 2a - 60288-2758 include homopolymers or copolymers prepared from monomer C=C and/or A
C-C-R~-CaC wherein A may be: hydrogen; hydrocarbon such as alkyl, A

aryl, etc.; acyloxy (typified by -COOR); halide; etc. R" may be divalent hydrocarbon typified by alkylene, alkarylene, aralk~lene, cycloalkylene, arylene, etc. Illustrative of such monomers may be acrylates, methacrylates, vinyl halides (such as vinyl chloride), styrene, olefins such as ethylene, propylene, butylene, dienes such as butadiene, isoprene, hexadiene, ethylidene norbornene; etc.
Although homopolymers of olefins (such as polyethylene, polypropyl-ene, polyisobutylene, etc.) or copolymers of ethylene with e.g.butylene and higher olefins may be employed, the preferred carbon-carbon backbone polymers include those selected from the group con-sisting of ethylene-propylene copolymers (EPM or EPR) - 2a -,~ ,.
. .~. .

,. ,. : .

~ 3~8 and ethylene-propylene-diene third monomer terpolymers IEpDM or EPT).

When the charge polymer i5 an ethylene-propylene copolymer (EPM also called EPR polymers~, it may be formed by copolymerization of ethylene and propylene under known conditions, preferably Ziegler-Natta reaction conditions. The preferred EPM copolymers contain units derived ~rom the ekhylene in amoun~ o~ 40-70 mole %, preferably 50-60 mole %, say 55 mole %, the r~mainder being derived from propylene.

The molecular weight Mn of the EPM copolymers which may be employed may be 10,000-1,000,000, preferably 20,000-200,000, say 100,000. The molecular weight distribution may be characterized by MW/Mn o~ less ~han about 15, preferably 1.5-10, say 2.

Illu~trative EPM copolymers which may be employed in practice of the proceYs of thiR invention may be those set forth in the following table, the ~ir~t li~ted being preferred:

~`~ A. The Epsyn brand of EPM marketed by Copolymèr Rubber and Chemical Corp., con~aining 60 mole ~ of units derived from eth~lène and 40 mole % of unit~ derived from prop~lene and having a Fln of 140,000 and a polydisper ity index MW/Mn of 1.6;
B. The ~pcar 505 brand of EP~I marke~ed by B. ~. Goodrich Co., containing 50 mole ~ of units derived from ethylene and 50 mole % of unit~ derived ~rom propylene and having a Mn f 25,000 and a polydispersity index of 2.5.
C~ ~he Esprene~ brand of EPR marketed by Sumitomo Chemical Co., containing SS mole ~ of units derive~ ~rom ethylene and 45 mole ~ of unit~ deri~ed from propylene and having a H~ of 25,000 and polydispersity index of 2-.5;

~hen the charye polymer is a terpolymer of ethylene-propylene-third monomer IEPT or EP~M), it may be formed by copolymerization of e~hylene~ propylene and third * ~a ~ k _3_ ~27~ L8 monomer. The third monome,r i5 commonly a non-conjugated diene typified by dicyclopentadiene; 1,4-hexadiene; or ethylidene norbornene. PolymerizAtion is effected under known conditions generally comparable to those employed in preparing the EPM
products. The preferred terpolymers contain units derived from ethylene in amount of 40-70 mole %, preferably 50-65 mole %, say 60 mole % and units derived from the pxopylene in amount o 20-60 mole %, preferably 30-50 mole %, say 38 mole % and units derived from diene third monomer in amounk o~ 0~5-15 mol~ ~, preferably 1-10 mole ~, say 2 male ~. The molecular weight Mn of the terpolymers may typically be 10,000~1,000,000, preferably 20,00~-200,~00, say 30,000. Molecular weight distribution of the useful polymers is preferably narxow viz a MW/Mn of typically less than 15, preferably 1.5-10, say 2.

Illustrative EPT-terpolymers which may be employed in practice of the process of this invention may be those set forth in the ollowing table, the firs~ ted being preferred.

TABLE
A. The Epsyn 4006 brand of EPT marketed by Copolymer Rub~er and Chemical Corp., containing 58 mole ~ of units derived from ethylene, 40 mole ~ of unit~ derived from propylene, and 2 mole ~ of units derived from ethylidene norbornene and having a Mn of 120,000 and a poIydispersity index MW/Mn of 2.2.
' B. The Ortholeum 5655 brand of EPT marketed by UuPont containing 62 mole % of unitq derived from ethylene, 36 mole %
of uni'ts derived from propylene, and 2 mole % of units derived ~rom 1,4-hexadiene and having a Mn of 80,000 and a polydispersity index MW/Mn o~ 2~ .
C. The Ortholeum 2052 brand of EPT marketed by DuPont containins 62 mole ~ of units derived from ethylene, 36 mole ~
35 of units derived from propylene, and 2 mole % of units derived from 1,4-hexadiene and having a Mn of 35l000 and a - polydispersity index MW/Mn of 2.
* ~C~ ~Rrk _4_ ~L2~79~
. . ,~
- D. The Royalene brand of EPT marketed by Unir~val containing 60 mole % of units derived from ethylene, 37 mole ~
of units derived from pxopylene, and 3 mole % of units derived from dicyclopentadiene and having a ~ln o 100,000 and a polydispersity index MW/Mn of 2.5.
E. Tha Epsyn 40A brand o~ EPT marketed by Copolymer Rubber and Chemical Corp., containing 60 mole % o~ units deri~ed from ethylene, 37 mole ~ of units de~i~ed from propylene, and 3 mole -~ of units derived ~rom ethylldene norbornene and having a Mn of 140,000 and a polydLsperslty index MW/Mn of 2.

The EPM and EPT polymers may contain minor portions ~typically le~ than about 30%) o~ other units derived from other copolymerizable monomers.

I~ is a fea~ure of the process of this invention that there may be grafted onto these oil-soluble, substantially linear carbon-carbon, backbon2 polymers, graft units derived func~ional units dexived from the reaction produce of (i) an ethylenically unsaturated aldehyde or ketone and (ii) a primary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring.
The carb~nyl compounds (aldehydes or ketones) which may be used in practice of the process of this invention may be charact~rized by the formula:

R-C-R' In the above formula, R may be hydrogen or a hydrocarbon selected from the group consisting of alkyl, aralkyl, cycloalkyl aryl, alkaryl, and alkenyl including such radicals when inertly substituted. When R is alkyl, it may typically be methyl, ethyl, n-propyl, iso-propyl, n-butyl, -- ~ ~a~rk _5- 3 ~793~
i-butyl, sec-buty, amyl, octyl, decyl, octadecyl, etc. When R
i~ aralkyl, i~ may typically be benzyl, beta-phenylethyl, etc.
When R is cycloalkyl it may typically b~ cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcycloheptyl, 3-butylcyclohexyl, 3-methylcyclohexyl, etc. When R is aryl, it may typically be phenyl, naphthyl, etc. When R is alkaryl, it may typically be tolyl, xylyl, etc. When R ls alkenyl, it may typically be vinyl, allyl, l-butenyl, etc. R may be iner~ly substituted i.e. it may bear a non-rea~tive substituent such as alkyl, aryl, cycloalkyl, etc. Typically inertly substituted R
qroups may include 3-chloropropyl, 2-ethoxyethyl, carboethoxymethyl, 4-~thyl cyclohexyl, etc. The preferred.R
groups may be lower alkenyl, i.e. C2 -C10 alkenyl, groups including e.g 7 ethenylO n-propenyl, butenyl, etc. R may preferably be butenyl.
R' may be selected from the same group as is R. R
and R' group~ may be cyclizea a~ in cyclohexenone. At least one of R and R' i an ethylenically unsaturated hydrocarbonO

The ethylenically unsaturated carbonyl compound may be a ketone or more preferably an aldehyde. When the compound is an ethylenically unsatura~ed ketone, it may have the formula R CO R'. Typical ketones may be a~ set forth in the following table:

12~33~ ~3 TABLE

benzalacetophenone buten-l-one-3 haxen~ one-3 3-penten-2 one l-hexen-3-one . 5~hexen-2-one Wh~n the carbonyl compound i~ an ethylenically unsaturated aldehyde as in ~he preferred ~mbodim~n~, it may have the formula RCHO. Typical unsaturated aldehydes may be as ~et forth in the following table:

TA:~3LE

crotonaldehyde cinnamaldehyde acrolein me~hacrolein The amine (which may be reacted with the ~thylenically unsaturated a}dehyde or ketone) may be a primary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring. Typical compound-q include ~hose bearing:
pendant primary amine groups, typified ~y N-(3-aminopropyl) morpholine~ pendan~ secondary amine groups, typified by N-(3 propylaminopropyl) morpholine7 in-ring ~econdary amine groups, typified by pipera~ine; etc.

It may commonly be characterized by the formula :
R* R** NH wherein R* and R** may be selected from the same group as that from which R may be select~d. At leask one of R*
and R** i~ other than hydrogen; and at least o~e of R* and R**:~
, ~ , - . ~ 7- .

. .
: .

3~3 contains a nitrogen atom in a heterocyclic ring. R* and R**
may be joined together in a cyclic configuration.
r When the amine is a primary amine, it may ~ypically be one of the folLowing:
TABLE

N-(3-aminopropyl) morpholine N-~3-aminopropyl)-2- pipecoline N-~3-aminopropyl~ pyrrolidone 2-ami~obenzothiazole 2-a~inopyrimidine 2-amino-3-picoline 4-amino-2,6-dimethyl pyrimidine When the amine is a secondary amlne, it may typically be one of the following:

TABLE
N-methylpiperazine morpholine pyrrolidine 2,6-dimethylmorpholine N-(betahydroxyethyl) piperaæine phenothiazine Thus in the preferred embodimen~, ~he functional monomer may be prepared by the reaction of an unsaturated aldohyde such as crotonaldehyde and a secondary amine which i~
free of unsaturation, such a~ pyrrolidine.
It i a feature of the process of thi~ invention in one of it~ aspect~ that the functional monomer compo~ n may be prepared by adding.to a reaction mixture ~i) a carbonyl compound, preferably an unsaturated aldehyde con~aining an ethylenically un~a.~urated carbon~caxbon double bond, (iii a ~7~3~8 - primary ox secondary amine, pre~erably a heterocyclic amine containing at least one nitrogen atom in the heterocyclic ring, and (iii~ a basic catalys~ or a dehydrating agent.
The basic catalysts which may he employed in practice of this invention typically include those ~et forth in the following table:

TABLE

potasslum carbonate ~odium carbonate ~odium hydroxide potassium hydroxide tributylamine In on~ aspect o t~e invention, the ~unctional monomer compo~ltion may be prepared by adding to a reaction mixture ~i) substantially equimolar portions of carbonyl compound and amine, ~ii) optional solvent, which may t~pically be tetrahydro~uran, dimethylacetamide, dioxane, or octanol, and (iii) catalyst in amount of typically 5 100 w~ say 20 w% of the total of the reactants~ The reaction mixture is maintained at 0C-25C for 1-3 hours and the catalyst is 3eparated by filtration. The product may be purified by distillation under vacuum or it may be used without further purification.
According to another a~pect of this invention, a dehydrat~ng agent, typically a molecular sieve, may be employed. Typical of the dehydratlng agents which may be employed may be thoqe set forth in the following table:

TA~LE

molecular sieve 35 silica gel magnasium sulfate sodium sulfate .:
_ g _ , ~ :7~8 calcium chloride In this aspect of the invention, the desired product may be prepared by adding to a reaction mixture (i) substantially equimolar portion of carbonyl compound and amine, (ii) optional solvent which may be tetxahydrofuran, dimethylacet~mide, dioxane, or octanol, and (iiil dehydrating agent such as molecular sieve in amount of typically 10-100 w%, ~ay 30 ~J% of the total o the reactant~. The reac~ion mixture i8 maintained a~ 60C - 200C, say 100C for 1-3 hours wi~h agitation preferably under inert atmosphere such a~ nitrogen.
Work-up may be as for the technique using ba~ic catalys~.

lS It ls a feature of the process of this invention that the functional monomar composition may be graft polymerized onto a b ~e polymer typi~ied by a copolymer of ethylene-propylene (EPR or EPM) or a copolymer of ethylene-propylene-diene th~rd monomer (EPT or EPDMl~

In practice of this aspect of tha process of this invention, 100 part~ of charge EPM or EPT may be added to 100-1000 part~, say 300 part~ of ~olvent. Typical solvent may be a hydrocarbon solvent such as n-hPxane, n-heptane, tetrahydrofuran, or mineral oil. Preferred solvent may be a commercial hexane containin~ principally n-hexane isomers.
Reaction mixture may then be heated to reaction conditions of 60C-180C, preferably 150C--170C, say 155C at 15-300 psi~, pre~erably 180-220 p9ig, say 200 psig~

The unctional monomer, which is to ~erve as graft monomer, is admitted in amount of 1-40 parts, ~ay 10 parts, ollowed by a solution in. hydrocarbon o~ ~ree radical initiator. Typical free radical initiators may include dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, di~isopropyl peroxide,. azobisisobutyronitrile, etc. ~he solvent is preferably the same as that in which the EP~ or EPT is - ~7~3~
dissolved. The initiator may be added in amount of 0.2-10 parts, say 4 parts in O. ~-40 parts, say 16 parts of solvent.

The free-radical initiator may be admixed with the graft solvent, monomer, and the polymer at a temperature below th~ decomposition temperature of the initiator. Typically mixing may be carried out at below about 40C, preerably ~0C
to 40C, say 20C. The reaction mixture i~ then raised to a tem~erature at least as high as ~he decompo~ition temperature of the initiator, typically 60C or higher.

- Reac~ion is typically carried out at 60C-180~C, say 155C and 180-220 psig, ~ay 200 psig during which time graft polymerizatisn of the aminP onto the base ~PM or EPT polymer occurs. The final product graft polym~r may be characterized by the presence of the units derived from graft monomer on the backbone polymer.

TYP1Ga11Y there may be one unit derived from graft monomer per 12.5 - 10,000, ~ay 167 carbon atom~ ~he charge backbone polymer. Alternatively expre~sed, there may be 0.1 -80, s~y 6 graft units pex 1000 carbon atoms of polymer backbone.

For ease of handling, the polymerization solvent may be exchange~ wi~h a heavier solvent such as SUS 100 oil.
Product graft polymer i9 typically obtain~d as a solution of 6-12 part3, say 8.5 parts thereof in 88-94 parts, say 91.S
parts of ~olvent.
The product 90 formed may be an oil-soluble, substantially lin~ar, carbon-carbon hackbone polymer of molecular weight Mn of 10, 000-1, 000, 000, preferably 20,000-200,000, say 80,000, having graf~ polymeriz~d thereon (per 1000 carbon atoms of polymer backgone) 0.1 - 80 units, preferably 1 - lS units, say 6 units derived from graft monomer.

~2~3~

Lubricating oils in which the dispersant viscosity index impro~ers of this invention may find use may include automotive, aixcraft, marine, railway, etc., oils; oils used in spark ignition or compression igni~ion englnes; summer or winter oil~t etc. Typically the lubxicati~g oil~ may be characterized by an ibp.o~ 570F-660F, ~ay 610F; an ep o~
750F-1200F, say 1020F; and an API gravity of 25-31, say 29~
A typical lubricating oil in which ~he polymer of this invention may be present may be a standard SAE 5W-30 hydrocarbon motor oil ~ormulation having the following composition:
TABLE

~%

3ase Oil 82 -Viscosity Index Improver 9 (10 w% ethylene-propylene copolymer in 90%
- 25 inert oil) -Standard Additive Package- 9 Poly~sobutenyl (Mn 1290) succinimide (dispersant);
calcium sulfonate (detergent);
Zinc dithiophosphate ~anti-wear);
di-nonyl diphenyl amine (anti-oxidant);
4,4'-methylene-bis ~2,~-di~t-butyl phenol) (antioxidant);

~7~
Use of the additive of this invention makes it possible to readily increase the viscosity index by 25-40 units, say 35 units and to obtain improved ratings on the tests measuring the dispersancy of the system. The viscosity index is determined by ASTM Test D-445.

Dispersancy is determined by the Bench VC Test (BVCT). In ~his test, the turbidity of an oil containing an additive is measured a~ter heatiny the test oil to which has been added a standard blow-by. The result which correlates with dispersancy i9 compared to three reference standard~
~Excellent, Good and Fair), tes~ed simultaneously with the test sample. The numerical rating decreases with an inerease in di~persant f~ectiveness. Results similar ~o or lower than that of the Good Reference indicate ~ha~ the additive is a good candldate.

It is poss~ble to obtain product polymers which serve a~ multi-functional additive~ which permi~ attaiilment of a dispersant, anti-oxidant, ~iscosity index improver when added to a hydrocarbon lubricating oil or to a synthetic type lubricating oil.

It is a feature of this invention that the so-prepared graft polymers may find use in lubricating oils as dispersant, anti-oxidant, vlscosity index improvers when present in effective amount of 0.2-5 w%, preferably 0.4-3 w%, say 0.9 w~. ~

Practice of the process of this invention will be apparent to thosa 3killed in the art fxom the following examples wherein, as elsewhere in this specificationt all parts axe part~ hy weight unless otherwise set forth. Control examples are designated by an asterisk.

~2793~8 60288-2758 DESCRIPTION OF PREFERRED EMBODIMENTS
EXAMPLE I
In this example, there is added to a reaction mixture, equimolar portions oE crotonaldehyde (70 parts) and pyrroli~ine (71 parts). There is a:Lso added, as dehydrating agent, 70 parts of Aldridge* brand Grade 12, molecular sieve. The reaction mix-ture, under an inert nitro~en atmosphere, is heated with agitation to about 100~C for 2 hours. The mixture is then cooled to room temperature and filtered to remove catalyst. The product functional monomer is used as so prepared without further purification.
EXAMPLE II
To a mixture of equimolar portions of ~-methyl piper-azine (100 parts) and potassium carbonate (34 parts), maintained at minus 5C, there is added dropwise an equimolar portion (70 parts) of crotonaldehyde. The mixture is stirred at 0C for one hour and then at 25~C for 3 hours. The solid is removed by filtration; and the unreacted starting materials are removed by vacuum distillation. The product functional monomer so prepared is used without further purification.
XAMPLE III
In this example, the procedure of Example I is followed except that the amïne is ~-(3-aminopropyl) morpholine (144 parts~
(1 mole).
EXAMPLE I~
In this example, the procedure of Example I is foliowed except that the amine is 1-(3-amino-propyl)~2-pipecoline (156 parts) (1 mole).
* Trade-mark - 14 -~ 793~L8 EXAMPLE V

In this example, the functional monomer prodùct of Example I - the reaction product of crotonaldehyde and pyrrolidine ~ is grafted onto an e~hylene-propylene copolymer (EPM) Mn of 1~0,000, containing 60 mole % derived from ethylene and 40 mole ~ derived from propylene.
100 parts of ethylene-propylene copolymer, dissolved ~ in 400. par~ o SUN-148 mineral oil as gra~tiny ~olvent i~
10heated to 155C with stirring under nitrogen. 10 parts of the monomer product of Example I is added, followed by 4 parts of dicumyl peroxide dissolved in 12 par~3 of SU~-148 mineral oiL
grafting solvent. The mixture i~ stirred at 155C for one hour. Solvent Neutral Oil 100 ~SNO-100) is added to give a 15 ~olution containing 8.5 w% polymer; and ~his solution is used as an additive to lubrlcating oil without further treatment~

EXAMPLE VI

2~ In this example, th~ procadure o Example V is followed except that the copolymer employed i5 the Ortholeum 5655 brand of terpolymer of ethylene-propylene-1,4-hexadiene of molecular weight Mn of 75,000 and containing 64 mole % of units derived from propylene, 35 mole % of units derived from ethylene, and 1 mole % of units derived from 1,4-hexadi~ne.
EX~MP~E VII
.
In this Example, the procedure of Example V is followed except that ~he monomer grafted is the reaction product of equimolar amounts o~ crotonaldehyde and N-methylpiperazine.

~ ~70/~ ~aY~

: -15-- ~2791~3~8 EXAMPLE VIII

In this Example, the procedure of Example V i9 followed except that the backbone polymer is the same EPDM
polymer used in Example VI and the monomer grafted i5 the product of Example II.

EXAMPLE IX

In this Example, the procedure o~ Example V i5 followed excep~ that the monomer grafted i~ the product o~
Example III, khe reaction produc~ of crotonaldehyde and N- ~3-amino propyl) morpholine.

EXAMPLE X
In thi~ Example, the procedure of Example V is followed except that the monomer grafted i9 the product o Example IV, the reaction product o~ croton aldehyda and 1-(3-amino-propyl)-2-pipecoline.

EXAMPLES XI-XVI

In this serie~ of Example~, the additive products 2S prepared in Exampl2s V-X are added in amoun~ of lQ w~
(corresponding to 0.85 w~ of active ingredient) ~o a fully formulated ba~e blend containing the following components:
TABLE
Components W%
SN0-130~0il 75,~5 S~0-320~0il 21. 64 Zinc dithiopho~phate (anti-wear~ 1.12 Naugalu~e 438 Brand of 4,4'-di-nonyl-di-phenyl amin~ ~
o~æ ~ark -16-33~3 (anti-oxidant) 0.39 ~ `. Surchem 521~ rand of Mg Sul~onate (detergent) 1.50 ., ~, .
Silicone polymer ~anti-foamant) 150 ppm This oil had the ~ollowing properties:

TABLE

_ Property Value Vi3co~ity Kin 40C CS 31.S0 100C CS 5.36 Pour PointF ~5 A~h sulfated % (ASTM D-874)0.93 Phosphorus % ~X-ray) 0.11 Sulfur % (X-ray) total 0.40 ~inc ~ (X-ray) 0~12 ;
Magnesium % O.33 Cold Cranking Simulator (cEQ-18~C) 1660 . 1;~7~318 Each of the products of Examples V-X so formulated with the fully formulated base blend i5 subjected to the Bench vc Test (svcT) ~o determine their dispersàncy.

The results are as set forth in the following table:

T~3LE

Example Product Result Standards ExcellenttGood/Poor XI V 23J2 lOoO/29~9/7000 XII VI 23. 6 8 . 0/29 o 4/68 . 0 XIII VII 36.2 7.9/29.4/60.6 XIV VIII 16.3 8.0/29.4/68~0 XV IX 46. 5 12. 6/38 . 0/66 . 5 XVI X 35.4 2.9/25.4/60.6 ~ From this Table, it is clear tha~ the dispersant, viscosity index improvers of this invention have good di~persant activity. They co~pare favorably with the dispersant activi~y of curren~ commercial dispersan~ viscosity index improvers.
Although thi3 invsntion ha3 been illustrat~d by reference to specific embodiments, it will be apparent ~o tho`se ~skilled in the art ~ha~ various changes and modifications may be made which clearly faLl within the scope o~ this in~ention.
' '~

Claims

1. A graft polymer comprising an oil-soluble, substantially linear, carbon-carbon backbone polymer having graft polymerized thereon units derived from, as a functional monomer, the reaction product of (i) an ethylenically unsaturated aldehyde or ketone and (ii) a primary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring.

2. A graft polymer as claimed in claim 1 wherein said backbone polymer is a copolymer of ethylene-propylene or a terpolymer of ethylene-propylene-diene third monomer.

3. A graft polymer as claimed in claim 1 wherein the molecular weight ?n of said backbone polymer is 10,000-1,000,000.

4. A graft polymer as claimed in claim 1 wherein the molecular weight ?n of said backbone polymer is 20,000-200,000.

5. A graft polymer as claimed in claim 1 wherein said functional monomer is prepared from crotonaldehyde.

6. A graft polymer as claimed in claim 1 wherein said functional monomer is prepared from a secondary amine.

7. A graft polymer as claimed in claim 1 wherein said functional monomer is prepared from a primary amine.

8. A graft polymer as claimed in claim 1 wherein said functional monomer is prepared from a heterocyclic amine containing a secondary amine in a heterocyclic ring.

9. A graft polymer as claimed in claim 1 wherein said functional monomer is prepared from a piperazine.

10. A graft polymer as claimed in claim 1 wherein said functional monomer is prepared from 1-(3-aminopropyl)-2-pipecoline.

11. A graft polymer as claimed in claim 1 wherein said functional monomer is prepared from a pyrrolidine.

12. A graft polymer as claimed in claim 1 wherein said functional monomer is prepared from a N-methyl piperazine.

13. A graft polymer as claimed in claim 1 wherein said functional monomer is prepared from a N-3-aminopropyl) morpholine.

14. A graft polymer as claimed in claim 1 wherein said graft polymer contains, per 1000 carbon atoms in the backbone polymer, 0.1 - 80 units derived from functional monomer.

15. A graft polymer comprising an oil-soluble, substantially linear, carbon-carbon backbone polymer of molecular weight ?n of 10,000 - 1,000,000 selected from ethylene-propylene or from ethylene-propylene-third monomer backbone polymers, said backbone polymer having graft polymerized thereon units derived from the functional monom?r formed from (i) crotonaldehyde and (ii) N-methyl piperazine or pyrrolidine or N-(3 aminopropyl) morpholine or 1-(3-aminopropyl)-2-pipecoline.

16. The process for preparing a graft polymer which comprises intimately admixing in a reaction mixture (i) an oil-soluble, substantially linear, carbon-carbon backbone polymer, (ii), as a functional monomer, the reaction product of (i) an ethylenically unsaturated aldehyde or ketone and (ii) a primary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring, and (iii) a free radical initiator;

maintaining the temperature of the reaction mixture at a temperature at least as high as the decomposition temperature of said initiator thereby effecting decomposition of said initiator and graft polymerization of said functional monomer onto said backbone polymer to form graft polymer, and recovering said graft polymer.

17. The process for preparing a graft polymer as claimed in claim 16 wherein the molecular weight ?n of said backbone polymer is 10,000 - 1,000,000

18. The process for preparing a graft polymer as claimed in claim 16 wherein the molecular weiyht ?n of said backbone polymer is 20,000 - 200,000.

19. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from a carbonyl compound containing an ethylenically unsaturated double bond.

20. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from cinnamaldehyde.

21. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from crotonaldehyde.

22. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from a secondary amine.

23. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from a hetero-cyclic amine containing a secondary amine in a heterocyclic ring.

24. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from a primary amine.

25. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from a piperazine.

26. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from 1-(3-aminopropyl)-2-pipecoline.

27. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from a pyrrolidine.

28. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from N-methyl piperazine.

29. The process for preparing a graft polymer as claimed in claim 16 wherein said functional monomer is prepared from N-(3-aminopropyl) morpholine.

30. The process for preparing a graft polymer which comprises initially admixing in a reaction mixture (i) an oil-soluble, substantially linear, carbon-carbon backbone polymer of molecular weight ?n of 10,000-1,000,000 selected from ethylene-propylene or from ethylene-propylene-third monomer backbone poly-mers, (ii) as functional monomer the reaction product of crotonal-dehyde and N-methyl piperazine, pyrrolidine, N-(3-aminopropyl) morpholine or 1-(3-aminopropyl)-2-pipecoline, and (iii) a free radical initiator;
maintaining the temperature of the reaction mixture or a temperature at least as high as the decomposition temperature of said initiator thereby effecting decomposition of said initiator and graft polymerization of said functional monomer onto said backbone polymer to form graft polymer; and recovering said graft polymer.

31. A lubricating oil composition containing a major portion of a lubricating oil and a minor effective viscosity index im-proving amount of a graft polymer comprising an oil-soluble, sub-stantially linear, carbon-carbon backbone polymer having graft polymerized thereon units derived from, as a functional monomer, the reaction product of (i) an ethylenically unsaturated alde-hyde or ketone and (ii) a primary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring.

32. A lubricating oil composition as claimed in claim 31 wherein said backbone polymer is a copolymer of ethylene-propylene or a terpolymer of ethylene-propylene-diene third monomer.

33. A lubricating oil composition as claimed in claim 31 wherein the molecular weight ?n of said backbone polymer is 10,000-1,000,000.

34. A lubricating oil composition as claimed in claim 31 wherein the molecular weight ?n of said backbone polymer is 20,000-200,000.

35. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from cinnamyl aldehyde.

36. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from crotonaldehyde.

37. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from a secondary amine.

38. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from a heterocyclic amine containing a secondary amine in a heterocyclic ring.

39. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from a primary amine.

40. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from a piperazine.

41. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from 1-(3-aminopropyl)-2-pipecoline.

42. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from a pyrrolidine.

43. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from N-methyl piper-azine.

44. A lubricating oil composition as claimed in claim 31 wherein said functional monomer is prepared from N-(3-aminopropyl) morpholine.

45. A lubricating oil composition containing a major portion of a lubricating oil and a minor effective viscosity index improving portion of 0.2 - 5 w% of a graft polymer comprising an oil-soluble, substantially linear, carbon-carbon backbone poly-mer having graft polymerized thereon units derived from, as a functional monomer, the reaction product of (i) an ethylenically unsaturated aldehyde or ketone and (ii) a primary or secondary amine which contains at least one nitrogen atom in a heterocyclic ring.

46. The method which comprises forming a reaction mixture containing (i) a carbonyl compound containing an ethylenically unsaturated carbon-carbon double bond, (ii) an amine, and (iii) a basic catalyst or a dehydrating agent;
maintaining said reaction mixture at functional monomer-forming reaction conditions including temperature of 60°C - 200°C thereby forming functional monomer containing moieties derived from said carbonyl compound containing an ethylenically unsaturated carbon-carbon double bond and said amine; and recovering said functional monomer containing moieties derived from said carbonyl compound containing an ethylenically unsaturated carbon-carbon double bond and said amine.

47. The method claimed in claim 46 wherein said aldehyde is crotonaldehyde.

48. The method claimed in claim 46 wherein said amine is a secondary amine.

49. The method claimed in claim 46 wherein said amine is a primary amine.

50. The method claimed in claim 46 wherein said amine is a heterocyclic amine containing a secondary amine in a heterocyclic ring.

51. The method claimed in claim 46 wherein said amine is a piperazine.

52. The method claimed in claim 46 wherein said amine 1-(3-aminopropyl)-2-pipecoline

53. The method claimed in claim 46 wherein said amine is a pyrrolidine.

54. The method claimed in claim 46 wherein said amine is N-methyl piperazine.

55. The method claimed in claim 46 wherein said amine is N-(3-aminopropyl) morpholine.

56. A functional monomer prepared from (i) a carbonyl compound containing an ethylenically unsaturated carbon-carbon double bond and (ii) an amine in the presence of a base catalyst.

57. A functional monomer prepared from (i) a carbonyl compound containing an ethylenically unsaturated carbon-carbon double bond and (ii) an amine in the presence of a dehydrating agent.