CA1069936A

CA1069936A - Aminated polymeric additives for fuels and lubricants

Info

Publication number: CA1069936A
Application number: CA245,148A
Authority: CA
Inventors: Lawrence J. Engel; J. Brooke Gardiner
Original assignee: Exxon Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 1975-03-05
Filing date: 1976-02-05
Publication date: 1980-01-15
Also published as: JPS51111806A; FR2303065B1; DE2606823A1; DE2606823C2; JPS6045206B2; FR2303065A1; GB1538350A

Abstract

ABSTRACT OF THE DISCLOSURE

Hydrocarbon polymers, preferably copolymers having a degree of crystallinity of up to 25 weight percent, comprising about 2 to 98 mole percent ethylene and one or more C3 to C28 alpha-olefins, are mechanically grafted at elevated temperatures under an inert atmosphere to f?rm an aminated polymer which may thereafter be mechanically-oxidatively degraded at an elevated temperature in the presence of an oxygen-containing gas to form an aminated polymeric reaction product useful as sludge dispersant for fuels and lubricants. When the aminated polymers have A high molecular weight, they are also viscosity-index improvers with dispersant and/or pour point depressant activity.

Description

6993~

This invention relates to polymeric dispersant additives for lubricants and hydrocarbon fuels. When of higher molecular weight, the additives are also useful as multifunctional viscosity-index improvers for lubricants. More particularly, this invention relates to hydrocarbon polymers such as tertiary hydrogen~containing or alpha-olefin polymers and, in particular, ethylene copolymers having a degree o crystallinity of less than about 25 weight percent, as determined by X-ray or differential thermal analyses, and comprising from about 2 to 98 percent by weight of ethylene and one or more C3 to C28 alpha olefins, usual-ly propylene, which have been grafted by mechanical action as by intensive milling or extrusion at an elevated temperature and in an inert atmosphere but in the presence of an amine compound to form an aminated polymer which optionally is thereafter mechanic-ally-oxidatively degraded as by intensive milling or extrusion at an elevated temperature, usually in the absence of a solvent r or fluxing medium and in the presence of air or oxygen-containing gas, to form an aminated polymeric reaction product of reduced average molecular weight.
A variety of polymeric materials which incorporate nitrogen have been described in U.S. and foreign patents as dispersants or fuels and lubri~ants, and as viscosity index improvers for lubricants. For example:
U.S. Patent 3,076,791 improves the pour point depres-sant activity of polymeric V.I. improvers by suhjecting polymers and amines to shearing forces so as to effect degradation of the polymer whereby the pour point depressant activity was enhanced.
*

- 2 -. . , , ~. .. . . . : . .
, .. .~ , , ., ,. .. .
: - ' ~: , :. ... ' . , ' ~L~6~36 U.S. Patent 3~404,091 grafts polar monomers, such as acrylonitrile onto hydroperoxidized copolymers of ethylene and propylene.
U.S. Patent 3,404,092 reacts hydroxylated ethylene-propylene copolymers with isocyanates.
U.S. Patent 3,687,849 grafts various unsaturated mono-mers onto a degraded, hydroperoxidized, interpolymer of ethylene and propylene.
U.S. 3,769,216 shows an atactic (i.e., non-crystalline) copolymer of ethylene and propylene containing from 45 to 65 mole percent of ethylene, mechanlcally degraded in the presence of oxygen, followed by reaction with a polyamine.
U.S. 3,785,980 discloses t]he reaction product of an amine with a hydroperoxidized atactic copolymer of ethylene and propylene containing from 45 to 65 mole percent of ethylene.
Briti~h Patent 1,172,818 describes the preparation of lube oil additives by the condensation of an amine with an oxid-ized, e.g. ozonized, polymer.
Our copending Patent Application No. 229,377, filed June 16, 1975, is directed to amorphous copolymers having up to 80 mole percent ethylene which are oxidized by mastication in the presence of air, followed by reaction with a less than a stoichio- ;
metric amount o~ amine, e.g., tetraethylene pentamine.
In contrast to the prior art and our copending applica~
tion, it has been discovered that it is possible to mechanically induce amino-grafting of the polymer at elevated temperatures to provide without polymer degradation a useful aminated polymer having particular utility as sludge dispersants for fuels and lubricants and as a viscosity~index improver. This is achieved ~ _ 3 - . :., .......... .. ; ... .

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by mechanically shearing a hydrocarbon polymer to incorporate at least 0.001 w~ight percent nitrogen in said polymer in the absence of an oxygen-containing gas and in the presence of an amine com-pound, said polymer optimally being a copolymer of ethylene and one or more C3 to C28 alpha-olefin. If desired, thereafter, said polymer may be degraded mechanically-oxidatively in the absence of a solvent and in the presence of an oxygen-containing gas.
Both of said steps are usually carried out at elevated temperatures in the range of 95C. to 260C., preferably 130 to about 260 C., more preferably 150 to 200C., and for a time ranging from about 1/2 hour to 12 hours and preferably from 4 to 5 hours. The inert environment which is required should be free of oxygen, that is, r no substantial polymer oxidation should occur during the mechanic-ally induced grafting of the polymer. No substantial oxidation is defined for the purposes of this invention as the introduction of less than about 0.05 weight percent, preferably less than about 0.01 weight percent, of oxygen into the amino-grafted poly-mer. These novel aminated polymer additives will contain from about one-thousandth of a percent of nitrogen to a maximum 25 percent by weight of nitrogen. For the aminated polymeric addi-tives of higher number average molecular weight (Mn) of from about 10,000 to about 500,000 (useful for pour depressant and/or V.I. improving applications), the nitrogen content ranges from about 0.001 to 5 weight percent, preferably 0.01 to 0.5 weight percent; for additives of molecular weights (Mn) of less than about 10,000 (useful in pour depressant and/or dispersant), the nitrogen content ranges broadly from about 0.001 to 25 weight percent, pre~erably from 0,01 to 8 weight percent. The unique , " ~'' . :~ ' ,' :

advantages of the present invention include the features that there is no significant degradation of polymer chain length during the amino-grafting of the polymer and that the amount of nitrogen incorporated into the polymer appears limited only by the con-centration of the amine and the time and temperature of the mechanically induced grafting. The average molecular weight of the amino-grafted polymercan be adjusted, if desired, by the mechanical-oxidative degradation step independent of the step of amination.
While any hydrocarbon polymer, e.g. polyisobutylene, would be suitable for the use in this process, the preferred polymers are tertiary hydrogen-containing or alpha-olefin polymers, such as ethylene-propylene copolymers, polyethylene, polypropyl-ene! partially hydrogenated (random or block), polymers of sty-rene-butadiene, styrene-isoprene and styrene-butadiene-isoprene.
Particularly preferred are those copolymers contain-ing from about 2 to about 98 weight percent of ethylene and one or more C3 to C28 alpha olefins, preferably propylene, which have a degree of crystallinity of less than about 25 weight percent as determined by X-ray and di~ferential scanning calorimetry and have a weight average molecular weight (Mw) in the range of about 2,Q00 to a~out 800,000 and a number average molecular weight (Mn) in the range of about 700 to 250,000 and a ratio of MW/Mn of less than about 8. These ethylene copolymers may be readily prepared usiny soluble Ziegler-Natta catalyst compositions, which are well known in the art.
Suitable copolymers may be prepared in either batch :, , . ' : .:: ...
.: , , ,: . . -, :;,: : . ... .. " . , ~al69936 or continuous reactor systems. In common wi~h all Ziegler-Natta polymerizations, monomers, solvents and catalyst components are dried and freed from moisture, oxygen or other constitutents which are knownto be harmful to the ackivity of the catalyst system. The feed tanks, lines and reactors may be protected by blanketing with an inert dry gas, such as purified nitrogen.
Chain propagation r~arders or stoppers, such as hydrogen and anhydrous hydrogen chloride, may be fed continuously or intermit-tently to the reactor for the purpose of controlling the molecular weight within the desired limits and the degree of crystallinity known to be optimum for the end product.
In addtiion to ethylene and propylene which are avail-able commercially in a state of purity designated "polymerization grade", other olefins which are useful for the preparation of these copolymers include l-butene, 1-pentene, l-hexene and l-oc-tene. Branched-chain alpha-olefins, such as 5-methylpentene-1 and 6-methylheptene-1, may also be utilized as well as longer carbon chains.
Media for dissolving or dispersing the catalyst com- -ponents and copolymer reaction products, and for heat exchange,may be selectedfrom the general group of saturated petroleum hydro-carbons and halogenated hydrocarbons. C12 or lower, straight or branched chain hydrocarbons are preferred. However, C5 to Cg saturated alicyclic, or C6 to Cg aromatic hydrocarbons may be used with equal facility. Equally useful are halogenated hydrocarbons having two to six carbon atoms in the molecule. Representative examples of solvents, which are also useful for removal of the - . .

~L~6~3i936 heat of reaction, include propane, butane, pentane, hexane, cyclopentane, heptane, cyclohexane, methyl cyclopentane, n-hep-tane, methyl cyclohexane, isooctane, benzene, toluene, mixed xylenes, sym-dichloroethane, trichloroethane and ortho-dichloro-ethane.
Principal Ziegler-Natta catalysts, useful in the synthesis of suitable copolymers of this invention, are selected from the group of transition metal compounds comprising Groups IVb, Vb and VIb of the Periodic Table of the Elements~ Particular-ly useful are compounds of vanadium and titanium. Most preferredare compounds of vanadium having the general formula VOzXt, wherein z has a value of 0 or 1, t has a value of 2 to 4 and X
is independently selected from the group consisting of halogens having an atomic number equal to or greater than 17 tCl, Br and I), acetylacetonates, haloacetylacetonates, alkoxides and haloalk-oxides. Nonlimiting examples of such catalysts are: VOC13;
VO(AcAc)2; VOC12(OBu); V(AcAc)3 and VOC12AcAc; where Bu is butyl and AcAc is an acetylacetonate.
Titanium compounds, which are best used in combination with vanadium compounds, have the general formula Ti(oR)4, where-in R is an acyclic, or alicyclic, monovalent hydrocarbon radical of 1 to 12 carbon atoms.
Most preferred among the principal catalysts are:
vanadyl trichloride (VOC13), and tetrabutyl titanate (Ti(OBu)4) used in combiantion with VoC13.
Ziegler-Natta cocatalysts, for use with the above principal catalysts, comprise organometallic reducing compounds from Groups IIa, IIb and IlIa of the Periodic Table of the Ele-~6~36 ments. Particularly useful are the organoaluminum compoundshaving the general formula AlR'mXn, wherein R' is a monovalent hydrocarbon radical selected from the group consisting of Cl to C12 alkyl; C6 to C12 alkylaryl and arylalkyl; and C5 to C12 cycloalkyl radicals, wherein m is a number from 1 to 3, X' is a halogen having an atomic number equal to or greater than,17, and the sum of m and n is equal to three.
Examples of useful cocatalysts are Al(Et)3; Al(isoBu)3;
EtAl(C1)2; Et2AlCl; and Et3A12C13.
The temperature at which the polymerization is con-clucted can influence the stabîlity of the catalyst species pre-sent in the reaction, with a corresponding influence on the rate of polymerization and the molecular weight of the polymer which is formed. Suitable temperaturesare in the range of -40C. to 100C., preferably 10C. to 80C., most preferably about 20 Cu to 6~C.
The pressure at which the polymerization is conducted will depend on the solvent, the temperature which is maintained in the reaction milieu and the rate that monomers are fed to the reactor. In the preferred temperature range, a pressure in the range of about 0 to 150 psig has given satisfactory results.
Molecular weight may be regulated by choice of solvent, monomer, principal catalyst concentration, temperature, the nature and amount of the cocatalyst, e~g., aluminum alkyl co-catalyst concentration, and whether a chain transfer reagent such as hydrogen is employed.
Polymerization may be effected to produce the high ethylene content copolymers used in the invention by passing 6~936 0.1 to 15, for example 5 parts of ethylene; 0.05 to 10, for example 2.5 parts of higher alpha-olefin, typically propylene;
and from 10 to 10,000 parts of hydrogen per million parts of ethylene; into 100 parts of an inert liquid solvent containing (a) from about 0.0017 to 0.017, for example 0.008~ parts of a transition metal principal catalyst, for example VOC13; and (b) from about 0.0084 to 0.084, for example 0.042 parts of co-catalyst, such as (C2H5)3 A12C13; at a temperature of about 25 C.
and a pressure of 60 psig. for a period of time suffici~nt to effect optimum conversion, for example, 15 minutes to one-half hour.
Since the reactivity of the higher alpha-olefin and rate in which it is incorporated into the copolymer is less than it is for ethylene, it is desirable to feed somewhat more than the theoretical proportions of higher alpha-olefin to obtain a copolymer having the desired ethylene content.
Conventional procedures, well known in the art may be used for recovery of the polymer from the reaction mixture leaving the reactor. The polymer "cement" issuing from the reactor may - 20 be quenched with a lower alcohol such as methanol or isopropanol.
A chelating agent can be added to solubilize the catalyst residues, and the polymer recovered as an aqueous slurry by steam stripping.
The resulting wet crumb may be purified by filtration, and then dried at a moderately elevated temperature under vacuum.
Useful amine compounds for grafting into the hydro-carbon polymers include mono and polyamines of about 2 to 60, e.g., 3 to 20, total carbon atoms and about 1 to 12, e.g., 2 to 6 nitrogen atoms in the molecule, which amines may be hydrocarbyl -~ :"' . "'; "" ' ";, ' . , ., ; :

6~3~36 amines or may be hydrocarbyl amines including other groups, e.g., hydroxy groups, alkoxy groups, amide groups, imidazoline groups and the like. Preferred amines are aliphatic saturated amines, including those of the general formulae:

R-N-R' and R-N-~CH2)S- [-N- (CH2) S- ~ -N-R

R" R' H R' wherein R, R' and ~" are independently selected from the group consisting of hydrogen; Cl to C25 straight or branched chain alkyl radicals; C1 to C12 alkoxy C2 to C6 alkylene radicals; C2 to C12 hydroxy or amino alkylene radicals; and Cl to C12 alkylamino C2 to C6 alkylene radicals; s is a number of from 2 to 6, preferably 2 to 4; and t is a number of from 0 to 10, preferably 2 to 6.
Examples of suitable amine compounds include:
mono-, di , and tri-tallow amines; 1,2-diaminoethane, 1,3-diamino-propane; 1,4-diaminobutane; 1,6-diaminohexane; diethylene triamine, triethylene tetraamine, tetraethylene pentamine; 1,2-propylene diamine; di-(1,2-propylene) triamine; di-(1,3-propylene) triamine;
N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine; NrN~di-(2-hydroxy-ethyl)-1,3-propylene diamine; 3-dodecyl-oxypropylamine; N-dodecyl-1,3-propane diamine, tris-hydroxymethyl methylamine, diisopropanol amine, and diethanol amine.
Other useful amine compounds include: alicyclic di-amines such as 1,4-di-(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines and N-aminoalkyl piper-azines of the general formula:

/CH2 ~ C~2 \
NH2-(CH2)p - N ~ N-G

' -- 10 --~L~6~936 wherein G is independently selected from the group consisting of hydrogen and J~-aminoalkylene radicals of from 1 to 3 carbon atoms;
and p is an integer of from 1 to 4. Examples of such amines in-clude 2-pentadecyl imidazoline, N-(2-aminoethyl) piperazine, N-(3-aminopropyl) piperazine, and N,N'-di-(2-aminoethyl) piperazine.
Commercial mixtures of amine compounds may advantage-ously be used. For example, one process for preparing alkylene amines involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylene-tetramine, tetraethylene pent-amine and isomeric piperazines. Low cost poly(ethylene amines) compounds having a composition approximating tetraethylene pent-amine are available commercially undex the trade mark Polyamine 400 tPA-400). Similar materials may be made by the polymerization of aziridine, 2-methyl aziridine and azetidine.
Still other amines separated by hetero atom chains, such as polyethers or sul~ides, can be used.
The grafting of polymers by mechanical means is old in the art. For the purposes of this invention, amino-grafting of the polymer may be done with a single piece of equipment, for example, e.g. a masticator, Banbury Mixer, rubber mill, extruder, homogenizer, etc. or may be done in stages with any of the said equipment. In the mechanically induced grafting device it is pre-~erred to operate in the absence of a solvent or fluxing oil so that the polymer is readily exposed to the amine and used in an inert envi-~6~3~i;

ronment, i.e., an environment which does not provoke any substan-tial oxidation of the polymer during the mechanical grafting step.
Useful equipment include Banbury mixers and mills having an ad-justable gap, which devices may be closed to contain the amine and jacketed to provide heat through a medium such as superatmospheric steam, or heated oil or Dowtherm. The amino-grafting reaction is primarily dependent upon temperature and shearing time. The nitrogen content of the aminated polymer can be determined by conventional analytical means such as by precipitating the polymer, separating the unreacted amine from the polymer and analyzing for nitrogen by the Kjeldahl technique.
When the amino-grafting reaction has reached the point at which the requisite level of nitrogen has been introduced into the polymer, a fluxing oil may be added to the aminated polymer.
Usually enough oil is added to providle a concentration of aminated polymer in the range of about S weight percent to about 50 weight percent based on the weight of the total resulting solution for subsequent oxidation~
Useful temperatures for amino-grafting the polymers are in the range from about 95 to 260C., preferably from about 150 to about 200C. The time required to achieve satisfactory results will depend on the type of mechanical shearing equipment, the temperature of the polymer and particularly the speed of rota-tion if using a blade mixer as the grinding or masticating device.
In this regard, we have found the Bramley Beken Blade Mixer to ~e particularly useful in providing in a single piece of equipment, the desired degree of amino grafting. This mixer, which i~
equipped with variable speed drive, has two rollers, fitted with , : : , ' .,; . ~' :

. .. .. . . . .

~9~3~;

helically disposed knives geared so that one roller revolves at one-half the speed of the other. The rollers are journaled in a jacketed reactor having two hemispherical halves in its base which conforms to the radii oE the two rollers. In this particu-lar mixer, one can vary the revolutions per minute of the rollers.
It has been found that the rpm of this masticator can vary from about 10 to about 150 for the faster roller and it is convenient to conduct the amino-grafting at a speed of about 52 for the fast roller and 26 for the slow roller. With the elevated temperature conditions set forth above, the time of mastication ranges from 0.5 to about 12 hours with from about 4 to about 5 hours found to be optimum. In carrying out the process of the invention, the environment for the mechanically induced amino-grafting of the polymer is to be inert, e.g., a nitrogen atmo6phere. The amine is added to the mechanical device after the oxygen has been re-moved from the polymer and from the environment in which the amino grating is to take place. This can be carried out, as for exam-ple, by mastication of the polymer under a nitrogen environment for upwards to 15 minutes so as to provide both the atmosphere free of oxygen and to remove from the polymer any occluded oxygen before introducing the amine compound into the system.
The amination can be conducted at pressures ranging from 0.1 to 20 atmospheres.
The amino-grafting step according to this invention can be accomplished without effecting chain length ~molecular weight) degradation of the aminated polymer. Measurement o~
molecular weights and degradation thereof was evaluated by deter-mination of the thickening efficiency of the polymer.

l: ;, ",~

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1~6993tii Thickening efficiency ~T.E.) is defined as the ratio of the weight percent of a polyisobutylene (sold by Exxon Chemical Co. as PARATONE* N) having a Staudinger Molecular Weight of 20,000, required to thicken a solvent extracted neutral oil, ~-having a viscosity of 150 SUS at 37.8C., a viscosity index of 105 and an ASTM pour point of 0 F., (Solvent 150 Neutral) to a viscosity of 12.4 centistokes at 98.9C., to the weight of a test copolymer required to thicken the same oil to the same vis-cosity at the same temperature.
The reduction in molecular weight of polymers by mechanical means is old in the art. The m~chanical-oxidative breakdown of the aminated copolymer may be done with a single piece of e~uipment, or may be done in stages with increasing in-tensity of the degree o~ breakdown which takes place. It is preferred to operate in the absence of solvent or fluxing oil so that aminated polymer is readily exposed to air. Useful equip-ment includes Banbury mixers and mills having adjustable gaps, which devices may be enclosed in jacketed containers through which a heating medlum may be passed such as superatmospheric steam. When mastication or breakdown has reached a desired level, as determined by oxygen uptake and reduction in thickening e~ficiency (T.E.) as defined before, a fluxing oil may be added to the degraded polymer. Usually enough oil is added to provide a concentration of degraded polymer in the range of about 5 welght percent to 50 weight percent based on the ~eight o~ the total resulti~g solution. The resulting oil solution may there-after be utilized as an article of commerce.

Useful temperatures for mechanical-oxidative degrading * Trade Mark ` ~6~936 ~

of the aminated polymers are in the range of about 95C to 260C.
The time required to achieve satisfactory results will depend on the type of degrading or mastication equipment, the temperature of degrading, and particularly the speed of rotation if using a blade mixer as the degrading or masticating device. In this regard, we have found the Bramley Beken Blade Mixer to be particularly use-ful in providing in a single piece of equipment, the desired degree of mastication, or milling and oxidative degradation. This mixer, which is equipped with a variable speed drive, has two rollers, fitted with helically disposed knives geared so that one roller revolves at one-half the speed of the other. The rollars are journaled in a jacketed reactor having two hemisperical halves -in its base, which conform to the rad:ii of the two rollers. Super-heated steam or heated DOWTHERM* may be circulated through the jacket to provide the desired temperature. With thi~ mixer satis-factory r~ductions in thickening efficiency may be obtained in from 0.25 to 20 hours in the temperature xange of about 95C to Another approach as earlier indicated is to carry out 2Q the mechanical-oxidative degradation in solution with ordinary stirring or gas mixing. This can be conveniently carried out by heating a solution in an inert solvent of the aminated polymer obtained at the conclusion of the amination step with oxygen or air. A mixture of oxygen and an inert gas such as nitrogen or carbon dioxide may be used. The inert gas then functions as a carrier of oxygen and often provides a convenient means of intro-ducing oxygen into the reaction mixture. The oxygen or air may be * Trade Mark ~6~g3~

introduced by bubbling through the polymer solution. However, it is frequently preferred to merely blow air over the surface of the solution while subjecting it to shearing agitation.
The inert solvent used in preparing the fluid solu-tion of the aminated polymer is preferably a liquid hydrocarbon such as naphtha, hexane, cyclohexane, dodecane, mineral oil, biphenyl, xylene or toluene, a lubrïcating oil, a chlorinated solvent such as dichlorobenzene, etc. The amount of the solvent is not critical so long as a sufficient amount is used to result in the fluid solution of the aminated polymer so as to facilitate the mechanical-oxidative degradation. Such a solution usually contains from about 50 to about 95 weight percent of the solvent.
The oil-soluble aminatedpolymeric additives of this invention can be incorporated in lubricating oil compositions, e.g., automotive or diesel crankcase lubricating oil, in concentra-tions within the range of about 0.01 l:o 20 weight percent, e.g., 0.1 to 15.0 weight percent, preferably 0.25 to 10.0 weight percent of the total composition. The lubricants to which the aminated products of this invention can be added include not only hydrocar-bon oil derived from petroleum, but also include synthetic lubri-cants such as- alkyl esters of dibasic acids; complex esters made by esterification of monobasic acids, polyglycols, dibasic acids and alcohols; esters of carbonic and phosphoric acids; carboxylic esters of polyglycols; etc.
These aminated polymeric additives can be advan-kageously incorporated in fuels, such as middle distillate fuels, at concentrations of from about 0.001 to about 0.5 ~69~36 1 weight percent and higherD pre~erably ~rom about 0.005 to 2 0o2 weight percent, of the tstal c~mposition. These aminat-

3 ed pol~meric addi~ives can contribute pour point depressant

4 and/or dispers~nt activity to the fuelO
The aminated polymers may be prepared in a con-6 centrate form~ e~g~, from about 20 weight percent to about 7 49 weigh~ percent in oil, eOgO, mineral lubricating oil, for 8 ease of handlingO
9 The above concentrates may contain other ronven 0 tional additives, such as dyes~ pour point depressants, 11 antiwear agents, antioxidants, other viscosity-index improv-12 ers, dispersants and the likeO

__ , 14 Six pounds of copol~mers o ethylene and propylene containing abcut 57 weight percent ethylene and having a T.E.
16 o~ 2.86 were put into a masticator which w~s a 205 gallon ~ -~
17 Bramley Beken Blade Mixer, fitted with a S ~.PO Reeves vari-18 speed motadrive geared to provide a speed at the mixer of 19 from about 13 to 150 rpm, ~he masticator was heated with a steam jacket to 177-202Co ~he copolymers were masticated 21 for about 15 minutes ~nder a nitrogen atmosphereO There~ -22 a f ter 11~5 grams of Polyamine 400 ~PA-400~ was added over a 23 15-minute period. The mas~ication wa~ continued with ~he 24 fast blade h~Ying an rpm o~ 100 and the slower blade having 25 an rpm of 50 which mastication continued for 3O5 hours under 26 the nitrogen bl~nket. The aminated reaction product showed 27 a T~Eo of 2.72. ~he ~nalysis of the produet indicated in-28 corporation oE 0.09 weight percent nitrogen into the polymer 29 and infrared ~bsorption indicated no oxidation.
EXAMPLE~ ~-5 ___ 31 Additional aminated-polymeric additives according 32 to the invention were prepared in accordance with the ~ 17 ~

. .

;9~3~

procedure and apparatus of Example 1 " except that the co- ~ :
2 polymers were different as indicated and the mastication at 3 52 rpm for the fast blade and 26 rpm for the slow blade. The 4 results are set forth in the following Table Io , ~ 18 ~

1~ 69 9 3 , :;

I o C~ O ~ O :, -~ :~ o o o o ~ -~ ~ :' , ~ o~
,~ ,~
o o o o o D

O
O > `.' ':
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a~ o ~
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~ a ~

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b Z; ~ ~ ~ ~
,,1 q~ o g' P~ O ~ ~ ~ , ~ ~ ~ :
q~ ~ I aa a~
~' ~C .a "3 ~ ~:

~ 19 -~69~3136 EX~MP~IE 6 2 Six pounds of copolymers o:f ethylene and propylene 3 having an ethylene content of about 55 weight percent and a 4 T~E, of 2086 was put into a masticator ~hich was a 2.5 gal-

5 lon Bramley Beken Blade Mixer, fitted with a 5 H.P. R~eves .

6 varispeed motodrive geared to provide a speed at the mixer

7 of from about 13 ~o 150 rpm. The masticator was heated with

8 a steam jacket to 140-152C and the 6 paunds of copolymer was masticated for about ~5 minutes under a nitrogen atmos- ~
0 phereO Thereafter 15 grams of diethylene tetraamine was ~:
ll added over a 15-minute period~ The mastication was contin- : .
12 ued with the fast blade having ~ rpm of 52 and the slower ~
13 blade having an rpm o~ 26 which mastieatlon continued for ~ . .. ;
l4 3.75 hours under the nitrogen bla~ketO At this time, a sam-ple o~ the amino-grafted polymer was analyzed and fou~d to 6 have a ToEo Of 2086 and a nitrogen content of 0.02 weight ~ ;
7 percent. Thereafter an air atmosphere was introduced to re~
8 place the nitrogen blanket. Mastication was then continued 19 at the above mechanical and temperature conditions of 160 186C for 3025 hours. A~ the end of ~he total run ~he To Eo 21 o~`the aminated oxy-degraded polymer, which had ~ ni~:rogen 22 con~ent of about 0002 weight percent had been reduced to loO~
23 EXAMPLES 7Dll 24 Five runs foLlowing the procedure of Example 6 were made using several other amine compounds. The results 26 of these five runs are set ~orth in Table II.

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1 The in~ention described herein has broader applica~ :
2 tlons th~n the dispersancy-sludge inhibition-VOI. improving 3 properties vf the reaction products that can be achieved 4 ~hrough ~he incorpora~ion o other moieties that would pro-vide other performance characteristics of lubricating oils 6 such as rust~inhibition, oxida~ive-s~ability, etcO Further 7 these moieties can be introduced to modify the physical and 8 chemical properties of the reaction products in non lubri-

9 cating oil appli¢ations ~o provide such peroxmance charac-0 teristics such as adhesion ~eOgO by means of acid function-11 ality) ~ dyeability, water shedding, polymer compatibility, etc~ Other ~ppllcations o~ the polymer additives are in 3 automatic transmission fluids, gear oils, industrial oils,4 etc.

Claims

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

1. In a process for aminating an olefin copolymer to form an oil-soluble aminated copolymer useful as a sludge-dispersing, viscosity index-improving additive for lubricating oil, the improve-ment which comprises carrying out said amination without substantial molecular weight degradation of said copolymer by mechanically working a mixture consisting essentially of amine and said copoly-mer, at a temperature of about 130° to 260°C., under an inert gas atmosphere, for about 0.5 to 12 hours to thereby incorporate about 0.01 to 0.5 weight percent nitrogen into said copolymer, wherein said copolymer is a copolymer having a number average molecular weight in the range of about 700 to 250,000 and consists essentially of ethylene in an amount in the range of 2 to 98 wt.%, and one or more C3 to C28 alpha-olefins, and wherein said amine is a saturated, aliphatic hydrocarbyl polyamine of 3 to 20 carbon atoms and 2 to 6 nitrogen atoms.

2. A process according to claim 1, wherein said amine has the general formulae:

; and wherein s is 2 to 6 and t is 0 to 10.

3. A process according to claim 1 wherein said aminated copolymer is thereafter mechanically-oxidatively degraded in the presence of an oxygen-containing gas and at a temperature in the range of about 95°C. to 260°C. for a period of from about 0.25 to 20 hours.

4. A process according to claims 1 or 3 wherein said amination temperature is about 150 to 200°C.

5. A process according to claims 1 or 3 wherein said amine is tetraethylene pentamine, diethylene triamine or triethylene tetraamine and said copolymer is an ethylene/propylene copolymer.

6. A process according to claims 1 or 3 wherein said copolymer is an ethylene/propylene copolymer, said amine is a polyethylene amine and wherein said degrading step is conducted in the absence of solvent or fluxing oil.