CA1134090A

CA1134090A - Non-cross linked products of hydrocarbon polymers with olefinic polar compounds and processes for making same

Info

Publication number: CA1134090A
Application number: CA304,268A
Authority: CA
Inventors: Donald R. Lachowicz
Original assignee: Texaco Development Corp
Current assignee: Texaco Development Corp
Priority date: 1977-07-28
Filing date: 1978-05-29
Publication date: 1982-10-19
Also published as: ES472119A1; DE2832406A1; BR7804866A; BE869377A; AU3733578A; IT1109480B; JPS5425902A; GB1601079A; FR2398795A1; NL7807830A; AU521904B2; ZA783399B; MX4953E; IT7826199A0

Abstract

ABSTRACT OF THE DISCLOSURE
This invention discloses novel, reaction products of ethylene-propylene copolymers, or ethylene-propylene nonconjugated diene terpolymers, with polar olefinic compounds, such reaction products being useful as deter-gent-dispersant-viscosity index improvers. Also disclosed are processes for their preparation and lubricating compositions containing such products.

Description

PIELD OF T~!E ~NVENTION
This invention discloses novel polymers of ethylene-propylene co-polymers, or ethylene-propylene nonconjugated diene terpolymers with polar olefinic compounds, such reaction products being useful as detergent-dispers-ant, viscosity index improvers. Also disclosed are processes for their prep-aration and lubricating compositions containing such products.
BACK_ROUND OF THE INVENTION
The rate of change of viscosity of lubricating oil wi~h temperature is called -the viscosity index or V.I. Oils having a high viscosity index ex-hibit a smaller change in viscosity with temperature variation than those with a low V.I. In such applications as automobile and aircraft engine lub-rications, where a wide range of temperature is encountered, lubricating oils having high viscosity indices are highly desirable and often critically nec-essary.
It is known that small quantities of long chain polymers of such hydrocarbons as isobutylene and similar aliphatic hydrocarbons, and of acryl-ates and methacrylates esters, will substantially increase the V.I. of pet-roleum lubricants. In particular, homopolymers and copolymers of methacrylic acid esters have been used extensively as "`V.I. improvers". These polymeric additives are usually prepared by the free radical polymerization of a mon-omer or a mixture of monomers. Polymers and copolymers of such esters as butyl methacrylate, hexyl methacrylate, dodecyl methacrylate and octadecyl ; methacrylate have been prepared by this method. Polymers of the lower alkyl methacrylates are generally good viscosity index lmprovers but are relative-ly insoluble in oil; the higher alkyl esters produce polymers which are more oil soluble but generally inferior ' i ' ., ' ~

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V.I. improvers. A copolymer of a lower alkyl methacrylate and a higher alkyl me-thacrylate will combine the desirable properties of its constituents, one portion providing the necessary oil solubility and the other contributing V.I. improvement to the oil. Copolymers with these properties are utilized extensively as V.I. improvers in lubricating oil.
Another type of additive commonly used in lubricating oils is the detergent-dispersant type. In the course of operating an internal combustion engine, products of oxidation of fuel and lubricant components are produced in the engine. These deleterious products tend to form sludge and varnish `` 10 deposits within the engine and generally have an adverse effect on engine operating efficiency; ultimately the build-up of such products can cause the engine to fail.
The purpose of the detergent-dispersant additives is to keep the deleterious material suspended in the oil, thus preventing deposit formation.
Examples of such detergent dispersants are the reaction products of low mol~
ecular weight (200-2000) polyolefins with ~a) P2S5, subsequently reacted with ethylene oxide, and ~b) maleic anhydride, subsecluently reacted with poly-ethyleneamines; these additives do not have the ability to improve viscosity index. The present invention relates to the preparation of novel additives having detergent-dispersant as well ~lS viscosity index-improving properties ~dual-purpose additives).
A previously proposed dual-purpose additive, described in United ` States Patent 3,7~5,980, is prepared by oxidation ~or hydroperoxidation) of an ethylene-propylene copolymer followed by subsequent reaction with an ' ~ amine. This additive suffers from disadvantages in that ~a) its preparation -~ requires two reaction steps which ~for commercial purposes) add processing ,; costs, compared with the one-step ! ~

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reaction required for the present invention; (b~ the flrst ~tep of the patented process i.~corporates oxygen functionq on~o ~he polymer bac~bone, making it more susceptible to participation in ~he delet~rious deposit-~orming proce~ses occurring under automotive engine opera~
tion than the additive of the p~esent in~ntion, which has only carbon and hydrogen attached to the polymer bac~one;
and (c) the product o the patented process tends to have an undesirably dark color. Anothe~ ~ual-purpose additive, 10 described in U~S. patent 3,40~,0gl, is made by oxidation of an ethylene~propylene-diene terpolymer and subsequent gra t polymer~zation reactia~ with acrylonitrile; this additi~e suffer~ ~rom the same above-men~ianed draw~acks as the additlve described in U.S. Pa~nt 3,785,980. This ~.
is ~lso ~he case for the additi~e d~scribed in U.S. Patent 3,687,849 or which, additionally, all examples must utilize an ethylene-propylene-diene terpolymer. The process of this invention is not so restricted and can use a saturated polymer such a~ an ethylene-propylene copolymer.
: 20 The products of the pr~sent invention re~uixe a sis~iicantly lower prOportiQn of polar olefinic compound for ~fec~ive detergent-dispersant properties ~han i5 de~cribed in the examples o U.S. Pate~ 3,687,849. Fur~her-mora, ~he weight ratios of polar ole~inic compound to fr~e radical iMitiator employed in the patent are relativ~ly high at about 11:1 and higher. By contra~t, the present inven-~ tion disclo~es the unexpected result that detergent~dispersant J effectivene~s is signific~ntly i roved whon much lower weight ratios of polar oleLinic ~ompound to initiator (less than about 7:1) are employed.
Unexpectedly, and ~uxprisingly,the products of ~his i~ention show no evidence of crosslinking which ~3~

would be expect~d when heati.ng the polymers in the presence of these initi-tiators. Such evidence, absent here, includes higher viscosity in solutions of the product or insolubility of the polymer in oil.
Other previously proposed dual-purpose additives are described and claimed in United States Patent 3,923,930. These additives comprise substan-tially linear hydrocarbon terpolymer backbone having grafted thereon poly-methacrylate polymers which are prepared by metallation techniques using alkyl lithium. In the absence of the unsaturated function, provided by the diene in the substrate polymer, the process of patent 3,923,930 is inoper-ative with a saturated ethylene-propylene copolymer (see D.P. Tate et al., "Metallation of Unsaturated Polymers and Formation of Graft Copolymers", J. Polymer Science, Part A-l, Vol. 9, 139-145 ~1971); referred to in the patent).
Additionally, there are several differences between the products of the patent and those of the present invention. Unsaturation is present in all products of the patent, but not in all products of this invention.
The patent discloses only alkyl methacrylate and dialkylaminoalkyl meth-acrylate moieties; the products of this invention have these and other ex-amples of unsaturated polar compounds. ~, In comparing the respective products, it should be noted that the unpurified patented product would never be considered for use because of the detrimental effects expected from the impurities, lithium compounds and the tetraalkylalkylene diamine. Advantageously, the present products can be used without purification.
This invention represents several substantial improvements, and otherwise differs from United States Patent 3,879,304. The patent requires utilization of an ethylene-propylene-diene terpolymer (having olefinic groups) while , ~ .
- 4 - .

-the present invention is not so restricted and can be carried out with ethylene-propylene copolymers (i.e., no third monomer included to incorporate unsaturation). The patent requires two separate reaction which (for commercial pruposes) adds processing costs, compared with the present invention which requires only one reaction. The above patent utilizes a lithium compound and a N,N,N'N'-tetra-alkylalkylene diamine. In addition to their relatively high cost, the use of these materials requires that the xeaction product must be purified before use to remove the diamine and by-product lithium compound which would be deleterious in the applications of the product. No such purification steps are required here in the present invention.
In Belgian Patent No. 844,761 filed July 30, 1976 and issued January 31, 1977 and German offenlegunsschrift No. 634,033 filed on July 29, 1976, corresponding to U. S.
Patent No.4,146,489, is disclosed a process for the preparation of a graft polymer of a co-polymeric hydrocarbon substrate and a nitrogen containing monomer characterized in that a liquid mixture of the hydrocarbon polymer, a polar nitrogen-containing monomer and a free-radical forming initiator is prepared under temperature conditions that prevent decomposition of the inltiator followed by raising of the temperature to decompose the initiator, and graft copolymers prepared by that process.
Examination of Offenlegunsschrift No. 643,033, hereinafter "No. 643,033", reveals several differences and deficiencies of that work compared with the present invention. Firstly, the graft copolymerization reaction of No. 634,033 led to increased thickening power of the product, and with it, a deterioration of the products shear stability (i.e., ability '~3 1. . I

to withstand mechanical shearing). Number 634,033 noted that this effect can be avoided~ but not without degradation of the desired dispersing abil-ity; it was found preferable to degrade, to a lower molecular weight, either the polymer substrate or the product graft copolymer. In the case of the present invention, on the other hand, no increase in thickening power~ or deterioration of shear stability, was observed. Second, all examples of No. 634,033 graft copolymer preparation were carried out with a weight ratio of monomer (or olefinic polar compound) to initiator of about 10:1. Lower ratios of these reagents were employed in the present invention, and the olefinic polar organic groups that become attached to the hydrocarbon poly-mer apparently do not constitute polymeric moieties, and the product is not considered a graft copolymer, in the sense that an increase in thickening power, through an increase of the polymer chain length, was not observed.
Further, reducing the ratio of olefinic polar compound to initiator caused ,, improvement in dispersing ability. Third, the products of No. 634,033 re-quire a higher nitrogen level for satisfactory dispersancy than those of the present invention. Material reported in No. 634,033 containing G.08% nitro-gen was described therein as a failed grafting product, while the products of the present invention are not so limited (i.e., higher or lower levels of nitrogen are satisfactory). Finally, No. G34~033 specifies that, in the preparation of the graft copolymer product, the liquid mixture of hydro-carbon polymer, olefinic polar organic compound, and initiator is prepared under temperature conditions which prevent decomposition of the initiator.
The process of the present invention is not so limited, and may be carried out either above or below the decomposition temperature of the , .~

i n i t i a t o r .
SUMMARY OF T~IE INVENT.ION
In accordance with this invention, there is pro- i vided a multipurpose lubricant additive comprising reaction products selected from a hydrocarbon polymer substrate of ~, the group consisting of an e-thylene~propylene copolymer, and1 ,1 an ethylene-propylene-diene terpolymer and mixtures thereof,¦
il with the terpolymer having an iodine number of about l to ,1 about 30, with the propylene content of the ethylene-propy-¦f lene copolymer and terpolymer being in the range of 20 to 76.5% by weight; and of a basic polar olefinic compound cha-il racterized by having an unsaturated portion capable of re-11 acting with a hydro-carbon polymer, as above defined, when il catalyzed by a free radical initiator, with the ratio of po-~lar ole~inic compound to initiator being from l:l to 8 the polar olefinic compound being incorporated in the addi-tive to the extent of at least l to 40 moles per lO0,000 grams of hydrocarbon po].ymer, the olefinic compound having the ~ormula /x ¦1 32C=c~ whereiD X is:

_R2 NR3R4 ~ ~ N ~ or a polynuclear aromatic amine and Y is 0 or NR5; Rl, R3, R
and R5 being hydrogen or alkyl; R2 being methylene or poly-methylene having from l to l6 carbon atoms in the chain; the Il olefinic compound being attached to the substrate in the I form of single units and in the form of chains of multiple ¦ units; these chains being too short, in the aggregate, to be considered polymeric in the sense that they do not cause an ¦ increase in the viscosity of a solution of the modified polymer relative to the viscosity obtained with a solution of the unmodified polymer substrate.

1l .

The products of this invention are viscosity indeximprovers useful as an additive for internal combustion engines or for other automotive parts, such as automotive -transmissions. This invention also relates to produc-ts made by this process and to lubricating compositions containing such products.
DETAILED DISCLOSURE OF THE INVENTION
Hydrocarbon polymers found to be useful for the purposes of this invention include ethylene-propylene co-polymers and ethylene-propylene-diene terpolymers having a reduced solution viscosity of about 0.3-4.0 or higher in decalin at 135C as well as hydrogenated styrene-conjugated diene copolymers in which examples of the conjugated diene include l,3-butadiene and isoprene. In the case of the terpolymers, the latter may have an iodine number of from l-30 and the diene monomer incorporated therein include, for example, either 5-alkylidene-2-norbornene or 1,4-alkadiene present at about 1.8-10 percent by weight of terpolymer.
Propylene content of either the ethylene-propylene copolymer or the ethylene-propylene-diene terpolymer may be in the range of 20-76~4 percent by weight.
Representative examples of terpolymers made with 1,4-alkadienes include: ethylene/propylene/1,4-hexadiene;
ethylene/propylene/1,4-dodecadiene; ethylene/propylene/-1,4-heptadiene; ethylene/propylene/6-mthyl-1,4-decadiene;

-7a ~, ~L~3~90 ethylene/propylene/1,4~tridecadiene; ethylene/propylene/7~7-dimethyl-1,4-octadiene.
Representative examples of terpolymers made with 5-alkylidene-2-norbornenes include: ethylene/propylene-5-methylidene-2-norbornene; ethyl-ene/propylene/5-ethylidene 2-norbornene; ethylene/propylene/5-isobutylidene-

2-norbornene; ethylene/propylene/5-n-heptylidene-2-norbornene, ethylene/
propylene/5-n-decylidene-2-norbornene; ethylene/propylene-5-n-dodecylidene-2-norbornene, ethylene/propylene/5-n-tridecylidene-2-norbornene; ethylene/
propylene/5-n-tetradecylidene-2-norbornene; and ethylene/propylene/5-hexa-decylidene-2-norbornene. Mixtures of two or more polymers chosen from among both ethylene-propylene and ethylene-propylene-diene polymers may be used if desired. A particularly preferred starting material is a commercially avail-able ethylene-propylene-5-ethylidene-2-norbornene terpolymer.
Preparation of the above-described terpolymers can be accomplished as set forth in United States Patent 3,151,173 by contacting ethylene, at least one alpha-olefin, and at least one S-alkylidene-2-norbornene in solu-tion in inert solvents with coordination catalysts, at temperatures between -20C and 70C, at atmospheric, subatmospheric or superatmospheric pressure and in the absence of catalyst poisons such as oxygen, water and carbon dioxide.
Examples of polar olefinic compounds suitable for reaction with the above-described polymers include dimethylamino ethyl acrylate and meth-acrylate, dimethylaminopropyl acrylamide and methacrylamide, 2- and 4-vinyl-pyridine, 2-dimethylamino-2-methylpropyl acrylate and methacrylate, 2- and 4-vinylquinoline, 2-aminoethyl acrylate and methacrylate, t-butylaminoethyl acrylate and methacrylate, N-vinyl morpholine, 2-ethylpyridinyl acrylate and methacrylate, and N-vinylin-dole. Reactions may be carried out with mixtures o~ polar olefinic compounds.
Principal requirements of such polar olefinic compounds are the presence of a basic primary, secondary or tertiary amine function and an un-saturated portion capable of undergoing an addition reaction with a hydrocar- `
bon when catalyzed by a free radical initiator:
~ I
R-H ~ C - C-~ R-C-C-H (R - alkyl or alkenyl). The polar olefinic com-pounds of this invention are included in, though not limited by, the following general formula: X

CH2 = C

wherein: X = -C-Y-R2-NR3R4; ~3 ; ~ ); and polynuclear aromatic amines Y = 0 or NR
R', R , R and R = H or alkyl R2 = methylene or polymethylene (Cl-C.16) The reaction with polar olefinic compou~ds (as described above) also may be carried out in the presence of acrylate-type esters of the type:
Rlc CH2 = C-C02R
wherein Rc is hydrogen or alkyl of from 1 to 3 inclusive carbon atoms as exem-plified by methyl, ethyl, propyl and isomers thereof, and Rd is alXyl of from 1 to 30 inclusive carbon atoms exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl~ nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl, eicosyl, docosyl, pentacosyl and ~3~

isomers and mixtures thereof. Inclusion of such acrylate-type esters in the reaction provides a product capable of improving the low temperature properties, .e~g., lowering the pour point, of lubricating oil formulations. .. :
Any of the typical free radical initiators, such as dicumyl peroxide, dibanzoyl peroxide, di-t-butyl peroxide, azobisisobutyronitrile, diacetyl peroxide, t-butyl-perace-tate and diisopropyl peroxidicarbonate may be employed in this invention.
Solvents for this reaction may include such inert .solvents as benzene, chlorobenzene and carbon tetrachloride, as well as hydrocarbon soIvents such as n-heptane, dodecane and hydrocarbon mixtures including mineral oils having a viscosity at lOOQF of about 10 to 200 SUS. Polymer concentra-tions in such solvents may range from about 2% to 60~ or higher.
Reactions typically are carried out under an inert atmosphere (e.g., nitrogen) at about 50 to 200~C, prefer-ably 60 to 160C, for periods of about 1-18 hours; re-action temperature and time are chosen according to thereactivity of the free radical initiator, lower reaction tempexatures or shorter reaction times being allowed for the more reactive initiators. Reactions may be carried out at a~mospheric pressure or above or below atmospheric.
The polymeric portion of the reaction mixture may be separated and isolated by any of the usual methods, such as precipitation with nonsolvents (e.g., acetone and iso-propyl alcohol) or stripp.ing solvent and other volatiles from the reaction mixture, and the polymeric product thus isolated may be used as the detergent-dispersant V~I.
improver (dual-purpose) additive; if convenient for blending purposes, the isolated polymeric product may be subsequently ~ ~ 3~1~9~

dissolved in a mineral oil, having a viscosity at 100F of about 10 to 100 SUS, to obtain a solutlon containing from about 2% to 60% polymer. Alternat-ively, such a polymer-oil solution may be obtained by either (a) using the oil as the reaction solvent, or (b) using a lower boiling reaction solvent ~such as benzene, chlorobenzene, heptane or decane), adding the oil to the reaction mixture, and isolating the polymer-oil solution by stripping the more volatile reaction solvent. Polymer-oil solutions thus prepared can be used without further purification as the dual-purpose additive.
The nitrogen content of the polymeric portion (after isolation by precipitation with acetone) of the dual-purpose additive of this invention generally is at least 0.01% to 0.4%, from which it is seen that the polar olefinic compound is incorporated to the extent of at least 1-40 mole per 100,000 g of hydrocarbon polymer, or higher. In addition to single units of olefinic polar compo~mds attached to the hydrocarbon polymer backbone, the latter also may have attached chains of multiple units; these chains being too short to be considered polymeric in the sense that, in the aggregate, they do not cause an increase in the viscosity of a solution of the modified polymer relative to the viscosity obtained with unmodified hydrocarbon poly-mer substrate, and thereby do not cause a degraclation of the polymer's shear stability (i.e., ability to withstand mechanical shearing) which would other-wise diminish the polymer's effectiveness as a VI improver.
In the finished lubricating oil compositions of the invention, there may be added also additional additives such as supplementary detergent dis-persants and V.I. improvers, oxidation inhibitors, corrosion inhibitors, anti-foamants, etc.

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Examples of the supplementary de-tergent dispersants contemplated herein are alkylsuccinimide, the ethylene oxide derivatives of inorganic phosphorus, acid-free, steam-hydrolyzed polyisobutene ~having a molecular weight of (700-5000) -P2S5 reaction product; and overbased calcium alkyl aro-matic sulfonate having a total base number at least abollt 300; and sulfurized normal calcium alkylphenolate. These supplementary detergent dispersants are disclosed in United States Patents 3,087,956, 3,549,534 and 3,537,966.
Examples of suitable antioxidants contemplated herein are zinc and calcium dialkyl dithiophosphate and diaryl dithiophosphates, the alkylated diphenyl amines, sulfurized alkylated diphenylamines, unsulfurized and sul-furized alkylphenols, phenolates and hindered phenols.
Examples of suitable corrosion inhibitors are zinc dialkyl dithio-phosphates, zinc diaryl dithiophqsphates, basic calcium, barium and magnesium sulfonates; calcium, barium and magnesium phenolates.
A widely used antifoamant can be included in the finished composi-tions of the invention; namely; the dimethylsilicone polymers, which are em-ployed in amounts of between about 1 and 1,000 ppm.
The various procedures for making the compositions of the invention are described in Exa~ples A-Z below.

EXAMPLE A
Into a round bottom flask equipped with mechanical stirrer, ther-mometer, gas inlet and reflux condenser were placed 25.0 g of ethylene propyl-ene copolymer having a molecular weight of 20,000 to 50,000 and 100 ml of chlorobenzene. The polymer was allowed to dissolve and the system was placed under a nitrogen ,J
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atmosphere. 1.57 g of dimethyl amino ethyl methacrylate (DMAEMA) and the initiator, dicumyl peroxide ~0.20 g), were added to the reaction flask and the mixture was heated, with stirring, at 130C for 6 hours. Samples were removed at various times to follow the progress of the reaction by nitrogen and infrared analyses of the polymer, which had been isolated by precipita-tion with hot acetone.
At the end of the six-hour reaction period most of the remaining reaction solution was added to 600 ml of hot acetone to precipitate the poly-mer. The latter was taken up in 150 ml of ben~ene and reprecipitated in 600 ml of hot acetone; this process was repeated to give a total of three precip-itations. After drying at 100C with full pump vacuum, the product (12.1) g had a nitrogen content of 0.025%. A Bench VC Test (BVCT) on a blend of the product at 1.5 wt % (net polymer) in oil showed that the product provided very good dispersancy. The BVCT rating for the blend was 8.5 (references:
4,52,62), compared with 97.0 (references: 4, 18, 40) for a like blend of the unreacted polymer. (The numerical~ parenthetical references are BVCT ratings of three standard dispersants; the mlmerical value of ratings decrease with increase in effectiveness). The Bench VC Test, above-mentioned, measures turbidity, the lower the turbidity values indicated below, the better dis-persancy. This test is carried out as follows:
Exact volumes of the test oil, a synthetic blowby, and a mineraloil diluent are mixed together in a test bottle. The bottle is then placed on a rocker and rocked for four hours at 280F. After heating, the sample is diluted with more mineral oil, cooled to room temperature, and the sample's turbidity is measured with a Lumetron turbidimeter equipped with a 700 milli-micron filter.

3~
Syn~hetic blowby is a hydrocar~on frac:tiorl which has been oxldiz~d under pecific conditions~ This material s:imulates the oxidized compounds w~ich find their way p st the piston rings and in~o the crankç:ase o~ a~ internal combus~ior e~gine ~
EX~DLE B
13.65 pounds of an ~thvlene/~ropvlene~5-ethylidene-2-norbornene te~polymer tor EPDM) available from Copolym~r Rubber and Chemical Corp), having a molecular weight o~ around 76,00~, were diss~lved ~n 92.0 pounds of a ~ineral oil having a viscosity of 145 SUS at 100F under a ni~rogen a~mosphere in a stainless steel reac~io~ ~essel.
To the solution was add~d DMAEMA (0.874 lbs) and dicumyl pero~ide tO.436 lb), and the mixture was heated at 140C
for 4 houxs ~der nitrogen at S psig in t}le sealed reactor.
105 pounds of a solvent neutral oil having ~ viscosity of 123-133 at 100F was added and t~e reaction mixture was stElpped under vacuum; a portion of the pxoduc~ was flltered through a 5-~cron car~ridge filter (63. 2 lb. recovered) 20 and the re~t was filtered through filter aid (125 . 8 lb.
ree::over~d ) .
The lat~er portion of the product was evalua~ed in th~ Bench ~C Test as the only ashle~s dispersant-det rgenl:
com~?onent at 12.0 w~. % in a fully fo~mulate~ lubricant oil and recaived a rating of 6~0 (re~er~nc~s: 2, 32,.76~.
The same pro~uct was also e~luated in a VC engine test at 18.0 wt. % in a fully formul~tPd lubricant oil which also contained a minor amount of a s~pplemental ashless detergent-dispersant ~alXenyl ~uccinimid~) at 3.5 wt. %;
resul~ing V~ engine ~est ra~ings were as follows: average sludge, 9.5; average ~arnish, a . 40; piston skirt varnish~
8.46. Corresponding minima ~o meet SE quali~y standards in this te~t are 8.5, 8.0 and 7.9 respectively. The product thus exceeded the sE standards.

EX~MPLE C-I
The procedure of these runs (summarized in Table I) was generally the same as that used in the previous Example A except that ~a) reactant ratios were varied, and ~b) instead of isolating the polymer, oil was added to the reaction mix~ure at the end of the reaction time, and solvent and any unreacted DMAEMA were stripped from the mixture with vacuum to yield a poly-mer-in-oil concen~rate (containing 10.0-17.5 wt % polymer). The latter con-centrate was filtered to improve clarity and then used to make blends in oil to contain 1.5 wt % neat polymer. The BVCT and thickening power data were obtained from these blends. The polymer was precipitated from small samples of the concentrates (using hot acetone to precipitate) for determination of polymer nitrogen content.
Examples A and C-H show reaction carried out in benzene of chloro-benzene solvents. In Examples J-~ an oil was used as the solvent. These ex-amples have an advantage over processes involving other solvents ~including processes of existing patents) in that the polymer-oil product mixture can be used as a lubricant without the added step of solvent exchange ~e.g., re-placement of benzene with oil).
EXAMPLE J
~0 Into a roun~ bottom flask equipped with mechanical stirrer, ther-mometer, gas inlet tube and reflux condenser were placed 60 g of mineral oil ~123-133 SUS at 100F) and 50 g of E-P copolymer having a reduced solution viscosity of about 0.6 in decalin at 135 C. The polymer was allowed to dis-solve and the system was placed under a nitrogen atmosphere. DMAEMA (2.0 g) rinsed in with 2.0 g of mineral oil (100 SUS at 100F) and the initiator, dicumyl peroxide ~L~L 3 ~a~

(l.0 g), were added to the reaction flask and the mixture was heated, with stirring, at 130C for 1~ hours. The reaction solution was diluted with the same mineral oil (138 g), and volatiles were stripped from the diluted solu-tion at lO0 C using a rotary evaporator and a vacuum pump. The solution was filtered to improve clarity. Nitrogen contents of the product solution, and of polymer isolated by precipitation, were analyzed to be 0.12 and 0.057%, respectively. The product solution blended at 12.5 wt % (2.5 wt % neat poly-mer basis) in mineral oil (123-133 SUS at 100F) had a thickening power of 23.0 SUS. The BVCT rating for the blend was 9.0 (references 2, 23, 69).
EXAMPLE K
The procedure of Example J was repeated except that lauroyl peroxide was substituted for dicumyl peroxide and the reaction was run at 75C instead of 130C.
EXAMPLE L
The procedure of Example J was repeated except that 4-vinylpyridine was substituted for DMAE~A.
EXAMPLE M
.
The procedure of Example J was repeated except that the mineral oil used as reaction solvent had a viscosity SUS of 145 at 100F.
EXAMPLE N
The procedure was the same as Example J except dimethylaminopropyl methacrylamide was substituted for DMAEMA.

The procedure was the same as Example J except that the reaction solvent was a mineral oil having a viscosity SUS of 100 at 100 F.

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EXAMPLE P
Same as ExamPle J except 2-(dimethylamino).2-methylpropyl methacrylate was substituted for D~AEMA.
EXAMPLE Q
The procedure used was the same as Example J
except that the E-P copolymer ~25.0 g) had a reduced solu-tion viscosity of about 1.15 in decalin at 135C, and the mineral oil solvent was incr~ased to 85.0 g.
EX~PLE R
Same as Example J except th~t 46.8 g of an.
ethylene/propylene/5-ethylidene-2-norbornene terpolymer (a) having a molecular weight of around 76,000 and a reduced solution viscosity of about 2.15 in decalin at 135C;
iodine number of 6 was used, (b) the amounts of mineral oil solvent, dicumyl peroxide and DMAEMA were increased to 313.2, 3.0 and 6.0 g, respectively, (c~ the reaction was r~l at 140C for 4 hours, (d) dilution was with 358 g mineral oil (100 SUS at 100~).
Test data for compositions C to $ are given in Table I and for compositions K to S in Table II.
These data show im~roved dispersancy as a result of the presence of the products of the invention.
EXAMPLE S
The pxocedure of Example J was repeated except for the following modifications: 360 g of a commercially available ethylene-propylene 1,4-hexadiene terpolymer dissolved in 1260 g of a mineral oil having a viscosity of 145 SUS at 100F was reacted in a round bottom flask under a nitrogen atmosphere at about 140C for 4 hours wi~h 16.0 g of DMAEMA rinsed in with 20 g of mineral oil, 100 SUS at 100F, and 8.0 g of dicumyl peroxide. The re-action solution was diluted with 1600 g of mineral oil ~3~

(100 SUS at 100F), s-tripped at about 140C in the reaction vessel with full pump vacuum, and filtered.
EXAMPLE T
Into a round bottom flask equipped with mechanical stirrer, ther-mometer, gas inlet tube and reflux condenser were placed 290 g of a commercial VI improver, consisting of about 13~ by weight of an E-P copolymer having a reduced solution viscosity of about 1~15 (in decalin at 135C) dissolved in a mineral oil solvent ~about 100 SUS at 100F), 6.0 g of DMAEMA, the latter rinsed in with 2.0 g of mineral oil solvent ~about 100 SUS at 100F), and 3.0 g of dicumyl peroxide. The stirred solution was placed under a nitrogen atmosphere and heated to about 140C. After maintaining this temperature for

4 hours, the solution was stripped at about 100C at full pump vacuum using a rotary evaporator and the solution was filtered.
EXAMPLE U
The procedure of Example T was repeated except that the amounts of DMAEMA and dicumyl peroxide used were 4.8 and 2.4 g, respectively.
EXAMPLE V
The procedure of Example T was repeated except that the amounts of DMAEMA and dicumyl peroxide used were 4.2 and 1.4 g, respectively.
EXAMPLE W
The procedure of Example T was used except that the amount of DMAEMA
and dicumyl peroxide used were 4.2 g and 0.6 g, respectively.
EXAMPLE X
The procedure of Example T was used except that the amounts of DMAEMA and dicumyl peroxide used were 3.2 .~.,.~

~L~3~

and 1.2 g, respectively, and the reaction was run at about 130C for 18 hours.
EXAMPLE Y
The procedure of Example R was used except that (a) the mineral oil reaction solvent had a viscosity of 145 SUS at 100F, (b) 3.0 g of DMAEMA and 1.5 g of dicumyl peroxide (the latter dissolved in 4.5 g of mineral oil, 100 SUS at 100F) were added to the polymer solution at the reaction temperature of about 140C and rinsed with 2.0 and 2.5 g respectively, of mineral oil (100 SUS at 100F), and (c) after heating at about 140C for 4 hours from the time of dicumyl peroxide addition, the reaction solution was diluted with 351 g of mineral oil (100 SUS at 100 F). After stripping and filtering, the product was tested in the BVCT at 12.0 and 6.0 wt % as the only ashless deter-gent-dispersant in a formulated motor oil test blend having a mineral oil (123-133 SUS at 100F) as the predominant component and minor amounts of an overbased calcium sulfonate detergent (1.53 wt %) a ~inc dialkyldithiophos-phate antioxidant (1.35 wt %), an alkyl diaryl amine antioxidant (0.25 wt %), a poly-(alkyl methacrylate) pour point depressant, (0.05 wt %), and a dialkyl silicone polymer anti-foamant (150 ppm). The BVCT ratings with 12.0 and 6.0 wt % product were 5.0 and 10.5, respectively, references for both tests were: 2.5, 17, 67. :

The procedure of Example Y was used except that 4.68 g of DMAEMA
and 0.26 g of dicumyl peroxide (dissolved in 1.0 g of mineral oil, 100 SUS at 100F) were added to the polymer solution at about 90 C, and rinsed with 3 g and 1 g, respectively, of mineral oil (100 SUS at 100F). After stirring at about 90C for 30 minutes, the temperature .~

~3~

o~ the reaction solution was increased to 150C over a 43 minute period. After 40 minutes at 1~0C, an additional solution of 0.26 g of dicumyl peroxide in 1.0 g of the same mineral oil was added and rinsed with l.0 g more of the mineral oil. After heating at 150C for l hour from the time fo the second addition of dicumyl peroxide solution, the reaction solution was diluted with 353 g of the same mineral oil ~lO0 ~US at 100F). After stripping and filtering, the product was tested in the BVCT at 12.0 and 6.0 wt. % as the only ashless detergent-dispersznt in the same test blend used in Example Y. The BVCT ratings with 12.0 nd 6.0 wt. ~ product were 13.0 and 32.0, respectively;
references for both tests were: 2.5, 17, 67.
''r~ EXAMPLE Z
The procedure of Example Y wals used except that 84.0 g of a commercially available hydrogenated styrene-butadiene copolymer (molecular weight of about 57,400;
styrene & butadiene mole ratio of aboul 48:52; iodine number of 6.7) was used in place of the ethylene/propylene/
~ S-ethylidene-2-norbornene terpolymer. The amounts of other materials were changed to the following: mineral oil solvent (145 SUS at lOO~F), 266 g; DMAEMA, 4.0 g; mineral oil to rinse latter~ 2.0 g; dicumyl peroxide, 2.0 g; mineral oil to make solution of latter, 6.0 g; mineral oil to rinse the peroxide solution, 4.0 g; mineral oil diluent (100 SUS
at 100F), 338 g. After stripping and filtering, the product is tested in the BVCT at 20.0 wt. ~ as the only ashless detergent dispersant in the same test blend used in Example Y. The BVCT rating was 19.5j the references were Z, 16, and 59.5.
The test data for Examples T-X are tabulated in Table III, below.

Among the advantageous features of this invention are the s.implicity and economy of the process and the fact that the reaction product are suitable for use without any purification treatment. Tllere is no need even for ,~.
stripping or filtration.

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Claims

The embodiments of the invention in which an ex-clusive property or privilege is claimed are defined as follows:

1. A multipurpose lubricant additive comprising reac-tion products selected from a hydrocarbon polymer substrate of the group consisting of an ethylene-propylene copolymer, an ethylene-propylene diene terpolymer and mixtures thereof, with the terpolymer having an iodine number of about 1 to about 30, and the propylene content of said ethylene-propylene copolymer and terpolymer being in the range of 20 to 76.5% by weight; and of a basic polar olefinic compound characterized by having an unsaturated portion capable of reacting with a hydrocarbon polymer, as above defined, when catalyzed by a free radical initiator, with the ratio of polar olefinic compound to initiator being from 1:1 to 8:1, said polar olefinic compound being incorporated in said ad-ditive to the extent of at least 1 to 40 moles per 100,000 grams of hydrocarbon polymer; said olefinic compound having the formula:

wherein X is:

or a polynuclear aromatic amine and Y is oxygen or NR5; with R1, R3, R4 and R5 being hydrogen or alkyl; andR2 being methylene or polymethylene having from 1 to 16 carbon atoms in the chain;
said olefinic compound being attached to said substrate in the form of single units and in the form of chains of multiple units; said chains being too short, in the aggregate, to be considered polymeric in the sense that they do not cause an increase in the viscosity of a solution of the modified polymer relative to the viscosity obtained with a solution of the unmodified polymer substrate.

2. The additive of Claim 1, wherein said hydro-carbon is derived from ethylene propylene and a non-con-jugated diene.

3. The additive of Claim 1, wherein said polar olefinic compound is selected from the group consisting of dimethyl-aminoethyl acrylate, dimethylaminoethyl methacrylate, di-methylaminopropyl acrylamide, dimethylaminopropyl methacry-lamide, 2-vinylpyridine, 4-vinylpyridine; 2-dimethylamino-2-methylpropyl acrylate, dimethylamino-2-methylpropyl methac-rylate, 2-vinylquinoline, 4-vinylquinoline; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, t-butylaminoethyl acrylate, t-butylaminoethyl methacrylate, N-vinylmorpholine, 2-ethylpyridinyl acrylate, 2-ethylpyridinyl methacrylate, N
vinylindole and mixtures thereof.

4. The additive of Claim 1, wherein said ter-polymer is selected from the group consisting of ethylene/
propylene/1,4-hexadiene; ethylene/propylene/1,4-dodecadiene;
ethylene/propylene/1,4-heptadiene; ethylene/propylene/6-methyl-1,4-decadiene; ethylene/propylene/1,4-tridecadiene;
ethylene/propylene/7,7-dimethyl-1,4-octadiene; ethylene/
propylene/5-methylidene-2-norbornene; ethylene/propylene 5-ethylidene-2-norbornene; ethylene/propylene/5-isobutyl-idene-2-norbornene; ethylene/propylene/5-n-heptylidene-2 norbornene; ethylene/propylene/5-n-decylidene-2-norbornene;
ethylene/propylene/5-n-dodecylidene-2-norbornene; ethylene/
propylene/5-n tridecylidene-2-norbornene; ethylene/propylene/
5-n-tetradecylidene-2-norbornene; ethylene/propylene/5-hexadecylidene-2-norbornene, and mixtures thereof.

5. The additive of Claim 1, wherein said hydro carbon polymer is an ethylene-propylene copolymer having a molecular weight of 20,000 to 50,000 and said olefinic com-pound is dimethylaminoethyl methacrylate.

6. The additive of Claim 1, wherein said polymer has a reduced solution viscosity of about 0.6 to 1.15 in decalin at 135°C.

7. The additive of Claim 1, wherein said hydro-carbon polymer is an ethylene propylene-5-ethylidene-2-norbornene terpolymer and said olefinic compound is dimethyl-aminoethyl methacrylate.

8. The additive of Claim 1, wherein said hydro-carbon is an ethylene-propylene copolymer having a reduced solution viscosity of about 0.6 in decalin at 135°C and said olefinic compound is 4-vinylpyridine.

9. The additive of Claim 1, wherein said hydro-carbon is an ethylene-propylene copolymer having a reduced solution viscosity of about 0.6 in decalin at 135°C and said olefinic compound is dimethylaminopropyl methacrylamide.

10. The additive of Claim 1, wherein said hydro-carbon is an ethylene-propylene copolymer having a reduced solution viscosity of about 0.6 in decalin at 135°C and said olefinic compound is 2-(dimethylamino)-2-methyl-propyl methacrylate.

11. The additive of Claim 7, wherein said ter-polymer has a molecular weight of around 76,000 a reduced solution viscosity of about 2.15 in decalin at 135°C and an iodine number of 6.

12. The additive of Claim 1, wherein said hydrocarbon is an ethylene-propylene-1,4-hexadiene terpolymer and said olefinic compound is dimethyl-aminoethyl methacrylate.

13. A process for making a multipurpose lubricating oil additive which comprises adding to a solvent, a hydrocarbon polymer substrate selected from the group consisting of ethylene-propylene copolymers, ethylene-propyl-ene-diene terpolymers and mixtures thereof, with the terpolymers having an iodine number of about 1 to about 30, and the propylene content of said ethylene-propylene copolymer and terpolymer being in the range of 20 to 76.4%
by weight; adding to the resulting solution a free radical initiator and a basic polar olefinic compound characterized by having an unsaturated portion capable of undergoing an addition reaction with a hydrocarbon polymer, as above defined, when catalyzed by said free radical initiator at a temperature of about 50 to 200°C the ratio of polar olefinic compound to initiator being from 1:1 to 8:1; said polar olefinic compound being incorporated in said ad-ditive to the extent of at least 1 to 40 moles per 100,000 grams of hydro-carbon polymer, said olefinic compound having the formula:

wherein X is:

or a polynuclear aromatic amine and Y is oxygen or NR5; with R1, R3, R4 and R5 being hydrogen or alkyl; and R being methylene or polymethylene having from 1 to 16 carbon atoms in the chain.

14. The process of Claim 13, wherein said hydro-carbon is derived from ethylene, propylene and a noncon-jugated diene.

15. The process of Claim 13, wherein said polar olefinic compound is selected from the group consisting of dimethyl-aminoethyl acrylate, dimethylaminoethyl methacrylate; di-methylaminopropyl acrylamide, dimethylaminopropyl methacry-lamide, 2-vinylpyridine, 4-vinylpyridine, 2-dimethylamino-2-methylpropyl acrylate, 2-dimethylamino-2-methylpropyl methacrylate; 2-vinylquinoline, 4-vinylquinoline; 2-amino-ethyl acrylate, 2-aminoethyl methacrylate; t-butylaminoethyl acrylate, t-butylaminoethyl methacrylate; N-vinylmorpholine, 2-ethylpyridinyl acrylate, 2-ethylpyridinyl methacrylate; N-vinylindole, and mixtures thereof.

16. The process of Claim 13, wherein said ter-polymer is selected from the group consisting of ethylene/
propylene/1,4-hexadiene; ethylene/propylene/1,4-dodecadiene;
ethylene/propylene/1,4-heptadiene; ethylene/propylene/6-methyl-1,4-decadiene; ethylene/propylene/1,4-tridecadiene;
ethylene/propylene/7,7-dimethyl-1,4-octadiene; ethylene/
propylene/5-methylidene-2-norbornene; ethylene/propylene 5-ethylidene-2-norbornene; ethylene/propylene/5-isobutyl-idene-2-norbornene; ethylene/propylene/5-n-heptylidene-2 norbornene; ethylene/propylene/5-n-decylidene-2-norbornene;
ethylene/propylene/5-n- dodecylidene-2-norbornene; ethylene/

propylene/5-n-tridecylidene-2-norbornene; ethylene/pro-pylene/5-n-tetradecylidene-2-norbornene; ethylene/pro-pylene/5-hexadecylidene-2-norbornene, and mixtures thereof.

17. The process of Claim 15, carried out in the presence of an acrylate-type ester of the formula:

wherein R is hydrogen or lower alkyl and Rd is an alkyl group having from 1 to 30 carbon atoms in the chain.

18. The process of Claim 13, carried out in the presence of a solvent of the group of benzene, chloroben-zene; n-heptane, dodecane and hydrocarbon mixtures having a viscosity at 100°F of about 10 to 200 SUS.

19. The process of Claim 13, further including the steps of isolating the polymeric product and dissolving same in a mineral oil having a viscosity at 100°F of about 10 to 200 SUS to form a solution containing from about 2% to about 60% by weight of polymer.

20. The process of Claim 13, comprising adding to the reaction mixture a mineral oil having a viscosity at 100°F of about 10 to 200 SUS and isolating a polymer-oil solution by stripping said reaction solvent from said mixture.

21. The process which comprises dissolving under a nitrogen atmosphere an ethylene/propylene/5-ethylidene-2-norbornene terpolymer having a molecular weight of about 76,000 and an iodine number of 6 in a mineral oil having a viscosity of about 100 SUS at 100°F; adding to the resulting solution dicumyl peroxide and dimethylaminoethyl methacrylate; with the ratio of said methacrylate to said peroxide being from 1.1 to 8:1; heating the resulting reaction mixture at about 140°C for about 4 hours, then adding to the resultant mass a solvent neutral oil having a viscosity of about 123 to 133 SUS at 100°F.

22. A lubricating composition comprising a major proportion of a petroleum base lubricating oil and admixed therewith 2-25 parts of an addi-tive according to Claim 1 per 100 parts of lubricating composition.

23. The composition according to Claim 22, wherein said additive is prepared by a reaction of an ethylene/propylene/5-ethylidene-2-norbornene terpolymer having a molecular weight of about 76,000 and an iodine number of 6 with dimethylaminoethyl methacrylate.

24. A multipurpose lubricating oil additive prepared by the process which comprises adding in a solvent, a hydrocarbon polymer substrate se-lected from the group consisting of ethylene-propylene copolymers, ethylene-propylene-diene terpolymers having an iodine number of about 1 to about 30, and mixtures of said substrates; the propylene content of said copolymer and terpolymer being in the range of 20 to 76.4% by weight; adding to the result-ing solution a free radical initiator and a basic polar olefinic compound characterized by having an unsaturated portion capable of undergoing an addi-tion reaction with a hydrocarbon polymer, as above defined, when catalyzed by said free radical initiator at a temperature of about 50° to 200°C the ratio of polar olefinic compound to initiator being from 1:1 to 8:1; said polar olefinic compound being incorporated in said additive to the extent of at least 1 to 40 moles per 100,000 grams of hydrocarbon polymer, said olefinic compound having the formula:

wherein X is:

; or a polynuclear aromatic amine and Y is oxygen or NR5; with R1, R3, R4 and R5 being hydrogen or alkyl; and R2 being methylene or polymethylene having from 1 to 16 carbon atoms in the chain.

25. A multipurpose lubricant additive consisting of the reaction product in the presence of dicumyl peroxide of an ethylene-propylene-1,4 hexadiene terpolymer having a molecular weight of 20,000 to 50,000 and an iodine number ranging from about 1 to about 30 and dimethylaminoethyl methacrylate, wherein the ratio of said methacrylate to said peroxide ranges from 1:1 to 8:1; said dimethylaminoethyl methacrylate being attached to said terpolymer in the form of single units and in the form of chains of multiple units;
said chains being too short, in the aggregate, to be considered polymeric in the sense that they do not cause an increase in the viscosity of a solution of the modified terpolymer relative to the viscosity obtained with a solution of the unmodified terpolymer.