US3445387A - Polar substituted polymers as detergents-viscosity index improvers - Google Patents

Description

United States Patent US. Cl. 25232.7 17 Claims ABSTRACT OF THE DISCLOSURE Terpolymers having two different l-olefins of from 2 to 6 carbon atoms and l-olefin of from 4 to 30 carbon atoms having at least one basic nitrogen atom at least ,6 to the olefinic carbon atom or a highly hindered basic nitrogen atom at least a to the olefinic carbon atom. The polymers have an intrinsic viscosity in the range of 0.2 to 1.5 dl./g. The polymers find use in lubricating oils for viscosity index improvement, acid neutralization and detergency.

Cross references to related applications This application is a continuation-in-part of applicatron Ser. No. 477,935, filed Aug. 6, 1965, now abandoned.

Background of the invention Field of the invention.Numerous additives are incorporated in lubricating oils used for internal combustion engines, not only to improve the lubrication by the oil, but also to provide the stable dispersion of sludges and other deposit-forming materials in the oil. Desirably, detergents and dispersants should not only be efiective under the hot conditions of the diesel engines, but also under the much more variable conditions of the automobile engine. In the relatively low temperature gasoline engine operation encountered in stop-and-go passenger car service, where fuel oxidation products are a major source of deposits. the use of lubricating oil detergents is particularly important.

Also, it is necessary that lubricating oils have a reasonable viscosity over a wide temperature range in order to provide proper lubrication. To achieve this result, viscosity index improvers are added to the lubricating oil. These agents ordinarily do not significantly affect the oil at low temperatures, but enhance the viscosity at high temperatures.

In detergents, it is also desirable that some acid neutralization 'be provided, since with sulfur containing fuels and lubricating oils, mineral acids are formed. These acidic materials are extremely corrosive, and neutralization reduces the corrosion and wear resulting from the acids.

Description of the prior art.-In the last ten years, numerous patents have been issued on ashless lubricating oil detergents. See, for example, U.S. Patents Nos. 3,219,666, 3,200,076 and 3,275,554. For the most part, these compositions have been based on the oil soluble polypropenyl or polyisobutenyl hydrocarbon group.

Other patents have issued disclosing amine modified polymers for use in lubricating oils. See, for example, US. Patent Nos. 2,794,312, 2,838,456, 3,092,563 and 3,125,462.

3,445,387 Patented May 20, 1969 Summary of the invention Terpolymers are provided having two different aliphatic hydrocarbon 1olefins of from 2 to 6 carbon atoms and one mono-substituted aliphatic hydrocarbon l-olefin of from 4 to 30 carbon atoms, wherein the monosubstituent has at least one basic nitrogen at least 8 to the double bond, except when the nitrogen atom is highly hindered. The basic nitrogen atoms are bonded solely to hydrogen, carbon, nitrogen and silicon atoms.

The polymers have an intrinsic viscosity in the range of about 0.2 to 1.5 dL/g. (as determined in Tetralin at C.).

When added to lubricating oils for use in internal combustion engines, the polymers provide detergency and dispersancy, viscosity index improvement and acid neutralization.

Description of the preferred embodiments The terpolymers of this invention have three olefins: two aliphatic hydrocarbon a-olefins of from 2 to 6 carbon atoms; and a third mono-substituted aliphatic hydrocarbon lZ-Olfifil'l of from 3 to 30 carbon atoms, the mono-substituent having at least one basic nitrogen atom. The polymers will have an intrinsic viscosity (as determined in Tetralin at 135 C.) in the range of about 0.2 to 1.5 dl./g., more usually in the range of about 0.4 to 1.2 dl./g. As estimated from the intrinsic viscosity measurements, based on a graph in the following reference, Moraglio, Chem. e ind. (Milano), 41, 989 (1959), polymers will have a molecular weight in the range of about 10,000 to 120,000, more usually in the range of about 16,000 to 90,000.

The hydrocarbon a-olefins of from 2 to 6 carbon atoms include ethylene, propylene, butene-l, 4-methylpentene-1, hexene-l, etc. Preferred olefins do not have a branch nearer than one carbon atom removed from the vinyl carbon atom, e.g., CHFCHCHZCE. Particularly preferred is the combination of ethylene and propylene.

The polymers will have from about 0.05 to 2 weight percent basic nitrogen, more usually from about 0.06 to 1 weight percent basic nitrogen. By basic nitrogen is intended which can be titrated with perchloric acid potentiometrically; usually the nitrogen will have a single or higher order of bonding (double or triple) to hydrogen, carbon, nitrogen, or silicon, most usually hydrogen or carbon; and the carbon, nitrogen or silicon to which the basic nitrogen is bonded will be bonded only to carbon or hydrogen. Usually, the nitrogen will be singly bonded to carbon and/ or hydrogen.

The basic nitrogen atom will be at least one carbon removed from the backbone of the polymer and then only when it is highly sterically hindered. (By highly sterically hindered is intended at least one group bonded to nitrogen having 3 carbon atoms bonded to the central atom (C or Si) which is bonded to nitrogen.) Otherwise, the basic nitrogen will be at least two carbons removed from the backbone of the polymer and preferably at least three carbons removed from the backbone of the polymer.

Generally, on the average there will be at least one amino substituted olefin per polymer molecule and more usually greater than one and fewer than ten. Most usually, on the average there will be more than one and fewer than five amino substituted olefins per polymer molecule. In evaluating the average, the amounts of polymeric material, if any, having no amine substituent, will not be included in the average. However, to the degree such nonamine substituted (hydrocarbon) polymers are present in the examples, the percent nitrogen reported will be reduced.

The polymers will for the most part have the following formula:

(C'Hr-(EII) (GHQ-CH) (CIIz-CPI R 1 ii in XY I:

wherein R and R are ditierent and are either hydrogen or lower alkyl of from 1 to 4 carbon atoms, usually of from 1 to 3 carbon atoms, i.e., methyl, ethyl or propyl. When alkyl, R and R may be branched or straight chain, preferably straight chain, and not branched at the a-carbon, i.e., the carbon atom bonded to the vinyl carbon is methylene.

X is alkylene of from 1 to 10 carbon atoms, most usually from 2 to 6 carbon atoms and Y is a basic nitrogen containing radical, generally of from to 16 carbon atoms, more usually of from 2 to 12 carbon atoms. Y may have up to 6 basic nitrogen atoms, but will generally only have from about 1 to basic nitrogen atoms, most usually as amino groups. Y may also have from 1 to 2 silicon atoms, the silicon generally bonded to nitrogen, and from 0 to 2 oxygen atoms.

I, m and n are the number percent of the individual monomers and add up to 100%. n as an average will generally be in the range of greater than 0.05 to 5%, preferably in the range of about 0.1 to 3%, and particularly preferred, 0.1 to 1%. I and m will generally each be in the range of about 25 to 75%, more usually in the range of about 30 to 70% and the sum of l+m will be in the range of about 95 to 99.95%, more usually in the range of about 97 to 99.9%.

Since the polymers of this invention are lubricating oil additives, they must be compatible with hydrocarbon lubricating oils over a wide temperature range. Also, the polymer must be compatible with a wide variety of oil additives. The subject polymer in order to be compatible, depending on the hydrocarbon olefin monomer combination, will have as indicated above at least 25 mol percent and, preferably, at least 30 mol percent of one monomer.

A preferred hydrocarbon monomer combination is ethylene and propylene. In this combination there should be less than about 70 mol percent ethylene (respectively 30% propylene), usually 40-70 mol percent ethylene and respectively 30-60 mol percent propylene. The preferred range for the monomers is 4560 mol percent ethylene and respectively 554O mol percent propylene.

The polymers are prepared with catalysts providing little, if any, stereoregularity. That is, the polymers will be amorphous-little or no crystallinity. The polymers are random as to the hydrocarbon monomers and, also preferably as to the containing monomers. These polymers will not create a haze with the common lubricating oils, e.g., Mid-Continent 100-200 neutral oils at usual additive concentrations (1-10 weight percent), even at low temerature, e.g., C. or below.

When referring to the various values, such as mol percent, it is intended that average values be understood. The mol percent should be relatively uniform over all the polymer molecules except at low nitrogen content. With decreasing nitrogen content, a limit is reached when hydrocarbon polymers-mo nitrogen containing monomer is incorporatedare obtained. The low nitrogen values do not reflect an increasing molecular Weight, but rather the presence of inert hydrocarbon polymers.

The hydrocarbon polymer affects the reported nitrogen and equivalent weight values which are determined from a nitrogen analysis on the total product.

The basic nitrogen containing olefin which may be incorporated directly or represents the monomer which may be introduced into the polymer by an indirect method, will have the following formula:

wherein X is an alkylene group of from 1 to 10 carbon atoms, more usually of from 2 to 6 carbon atoms, and Y is a basic nitrogen containing radical, usually bonded through a basic nitrogen to X. Y will ordinarily have from 0 to 16 carbon atoms, more usually from 2 to 12 carbon atoms, and most usually from 2 to 8 carbon atoms, will have from 1 to 6 basic nitrogen atoms, more usually from 1 to 5 basic nitrogen atoms and may have from 0 to 2 silicon atoms.

Also, oxygen may be present, as hydroxyl or ethereal groups bonded to carbon. Normally, from 1 to 2 oxygen atoms may be present. Except for the heterocyclic amine groups, the carbon atoms for the most part will be saturated aliphatic carbon atoms, although some aliphatic (olefinic) unsaturation may be present, with multiple bonding either to carbon or nitrogen; the carbon atoms may be present to form alkyl groups, alkenyl groups, or in combination with the nitrogen atoms, oxygen atoms or silicon atoms, heterocyclic rings having from 5 to 6 annular members. Y is usually free of aromatic unsaturation, although heterocyclic amines may contain aromatic unsaturation.

The first class of substituents will be the simple mono amine and its derivatives. The olefin having this monoamine substituent will for the most part have the following formula:

0 m=on wherein X is alkylene of from 1 to 10 carbon atoms, more usually from 2 to 6 carbon atoms, and preferably polymethylene of from 2 to 6 carbon atoms, and T and "I" may be the same or different. T and "I may be hydrogen, or hydrocarbon radicals of from 1 to 12 carbon atoms, more usually of from 1 to 8 carbon atoms, hydroxy or alkoxy hydrocarbon radicals of from 2 to 10 carbon atoms, more usually of from 2 to 8 carbon atoms, or trialkyl silyl radicals of from 3 to 12 carbon atoms, more usually of from 3 to 9 carbon atoms. For the most part, T and T will be hydrogen or saturated aliphatic hydrocarbon radicals of from 1 to 6 carbon atoms or saturated hydroxy or alkoxy aliphatic hydrocarbon radicals of from 2 to 6 carbon atoms.

Illustrative amino substituents are amino, methylamino, propylamino, dimethylamino, dihexylamino, hydroxyethylamino, di(hydroxyethyl)amino, methoxypropylamino, ditrimethylsilylamino, decylamino, etc.

A second group of amine substituted olefins are alkylene polyamines or polyalkylene polyamines having two or more basic nitrogen atoms, more usually from about 2 to 6 nitrogen atoms, and preferably from about 2 to 5 basic nitrogen atoms. These olefins will for the most part have the following formula:

wherein X is alkylene of from 2 to 10 carbon atoms, more usually of from 2 to 6 carbon atoms, and preferably polymethylene of from 2 to 6 carbon atoms, Z is alkylene of from 2 to 6 carbon atoms, more usually of from 2 to 3 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms, and p is an integer of from 1 to 5, more usually of from 1 to 4.

Illustrative alkylene polyamines and polyalkylene polyamines are ethylene diamine, diethylene triamine, triethylene, tetramine, tetraethylene pentamine, dipropylene triamine, hexamethylene diamine, tris(2-aminoethyl)amine, etc.

Equivalent to the alkylene polyamines are piperazines and aminoalkylene piperazines which are provided for in following formula.

Another group of basic nitrogen containing substituted monoolefins have the following formula:

wherein X is alkylene of from 2 to carbon atoms, more usually of from 2 to 6 carbon atoms, and preferably polymethylene of from 2 to 6 carbon atoms; for the symbols in parentheses, N and C have their ordinary meaning of nitrogen and carbon, respectively, A and D may be the same or different and are nitrogen or oxygen, a, c and e are integers of from 0 to 3, b and d are integers of from 0 to l, and the sum of a, b, c, d and e is in the range of 4 to 5. The bonds between the annular members may be single or alternating double, there being from 0 to 3 double bonds in the ring, and the valences of the annular members being satisfied by hydrogen, or from 0 to 3 substituents which may be lower alkyl, more usually alkyl of from 1 to 3 carbon atoms, amino, and aminoalkyl of from 2 to 3 carbon atoms. The total number of carbon atoms of the heterocyclic radical will not exceed 16 and usually will not exceed 8.

Illustrative heterocyclic radicals provided for by the above formulae are morpholine and alkyl substituted morpholines, piperazines such as piperazine, 2,6-diamino piperazine, N-2-aminoethyl piperazine, and N,N'-di(2- aminoethyl)piperazine; imidazolines such as imidazoline, N-(Z-aminoethyl imidazoline), and 4-methyl imidazoline; pyridines such as pyridine, 2 aminopyridine and 2,6- di(tert.-butyl)pyridine; and diazines and triazines such as 1,3-diaminotriazine, aminomethyl, diazine, etc.

Finally, nitrile substituted olefins and basic nitrogen derivatives thereof may also be used, the nitriles primarily as intermediates. These olefins have the following formulae:

'wherein X is alkylene of from 1 to 10 carbon atoms, more usually of from 2 to 6 carbon atoms, and preferably polymethylene; T and T are hydrocarbon radicals of from 1 to 6 carbon atoms, or hydrogen, more usually saturated aliphatic hydrocarbons of from 1 to 3 carbon atoms (alkyl); A is oxygen or nitrogen and Z and p are as defined previously.

The polymers of this invention can be prepared in a variety of ways. A preferred and novel method is to directly incorporate an amine containing a-olefin with 2 hydrocarbon olefins into a polymer. This can be achieved by using an alkyl aluminum or alkyl aluminum halide catalyst, e.g., alkyl aluminum sesquichloride, dialkyl aluminum chloride and trialkyl aluminum wherein the alkyl groups are of from 1 to 3 carbon atoms, preferably ethyl, with vanadium oxychloride. (The trialkyl aluminum may be used with activated titanium trichloride.)

The ratio of atoms of aluminum to atoms of vanadium is not particularly critical, there being from 2 to 20 atoms of aluminum per atoms of vanadium, usually from 2 to 10 atoms of aluminum per atoms of vanadium. Critical to the process is the ratio of amine containing olefin to aluminum. There should be not more than 1 mole of amine or basic nitrogen containing olefin per atom of aluminum in the catalyst and preferably there should be not more than 1 equivalent of basic nitrogen per atom of aluminum in the catalyst. Usually, there will be from about 0.1 to 1 equivalent of basic nitrogen per atom of aluminum in the catalyst.

The temperature for the reaction will generally be in the range of about 10 to 100 C. Depending on the monomers-gases or liquids at room temperature-the pressure may vary from atmospheric pressure to 100 psi.

The solvents used will generally be inert hydrocarbons which are liquids at the temperature of reaction. Illustrative solvents are heptane, octane, benzene, toluene, xylene, etc. The concentrations used will generally be about 1 mm. of aluminum in from about 0.10 to 5 liters of solvent.

The process is novel and may be used to form copolyberstwo monomers, or higher order polymers-terpolymers having three monomers. The hydrocarbon monomers will be a-olefins of from 2 to 6 carbon atoms. With gaseous a-olefins, the olefin is fed into the solvent at a convenient rate, while the liquid a-olefins, all of the olefins may be added initially or during the course of the polymerization, maintaining a proportionate concentration in solution of the aminoolefin.

Molecular weight of the polymer may be controlled by conventional means, e.g., hydrogen.

The product is worked up in the normal manner. The polymer is isolated and then extracted with methanol to remove catalyst residues and dried. Various modifications of this procedure are well known and appear in the literature.

By means of the above process, terpolymers are obtained which have excellent solubility in the hydrocarbon media in which, for the most part, they are employed.

Alternatively, a halo substituted olefin may be copolymerized with the desired hydrocarbon olefins and then the halogen displaced with a basic nitrogen compound. A method for preparing copolymers of hydrocarbon olefins and halohydrocarbon olefins is disclosed in copending application Ser. No. 304,958, filed Aug. 27, 1963. In that application, an organo-aluminum compound is used with either titanium trichloride or vanadium oxychloride and a Lewis base such as a tertiary amine or dialkyl ether.

The displacement reaction with the amines is generally carried out in an inert solvent. Suitable solvents include chlorobenzene, toluene, or higher boiling aromatic or chloroaromatic solvents, etc. Generally, the temperature will be in the range of about to 200 C. With volatile amines or solvents, pressures above atmospheric will be used to maintain the reaction mixture in the liquid state. Otherwise, atmospheric pressures will sulfice. The amount of amine used will be from about 1 to 10 moles per atom of bromine. The time for the reaction is dependent on the other variables, generally being in excess of one hour and usually not exceeding 24 hours.

The method of preparing the polymer should provide for its use as a lubricating oil additive. Generally, the methods described in this application using Ziegler-type" catalysts are preferred. These catalysts employ a Group III organo-metallic compound with either a titanium or vanadium halide or oxy compound giving nonstereoregular polymers.

The following examples are offered by way of illustration and not by way of limitation.

Example I Into a reaction flask was introduced 0.5 g. (-2 mm.) of ethyl aluminum sesquichloride, 0.05 g. (-0.6 mm.) of vanadium oxychloride, 300 ml. of dry n-heptane and 1.0 millimoles N-( 8-[1-octenyl] triethylene tetramine and the flask flushed with nitrogen. Into the resulting solution at room temperature was then introduced ethylene at a flow rate of 600 ml. per minute and propylene at a flow rate of 1,400 ml. per minute and the flow maintained for 30 minutes. At the end of this time, the catalyst was quenched with methanol, the precipitated polymer washed twice with methanolic hydrochloric acid, then with methanol, aqueous ammonium hydroxide, followed by methanol and acetone and then vacuum dried at 85 C. The yield was 7.1 g. Analysis: Wt. percent N=0.2S, 0.24; intrinsic viscosity (Tetralin at C.)=0.65 dl./g.

Following the procedure described above for batch preparations and using a variety of nitrogen substituted olefins and a mole ratio of ethylene to propylene of 6 to 14 (as in Example I), various products were prepared which are tabulated in the following table. The ethylene was introduced at a rate of 600 ml./min. and the propylene at a rate of 1,400 ml./min.

the sample to be tested. The viscosity measurements are determined at 210 F. and reported in SUS. The shear test TABLE I Analysis, Millimoles weight. Milli- Time, Temp, Yield, a percent Ex. No. Nitrogen containing monomer moles EASC l V0013 2 min. grams (dl/g.) N

II. Edimethylamino-octene-I 3.0 3. 4 3.0 30 25 11 1.8 0. 24 III de 3.0 3. 4 3.0 30 25 12. 1. 9 (I. 26 IV .110... 3. 0 3.4 3. 0 30 3. 7 2. ()5 0.16 V dc 3.0 3.4 3.0 25 8.1 2.08 0.29 VI N-allylhexaniethyldisilazane 2.0 2.0 0.3 30 25 3.1 0.23 VII S-triethyleno tetra-amino octane-l 0. 3 2.0 0.6 60 25 7. 1 0. 18 VIII 8-(N-(2-aminoethyl)-piperazine substituted) octane-1"... 1. 0 2.0 0. 6 30 25 4. 2 4. 41 0.33 IX .S-(diethylene triamino) octane-1 1. 0 2.0 0. 6 30 25 5. 3 0. 34 Scyano octene-l 1. 0 2 0. 6 30 0 9. 3 1.96 0. 06 Allylcya .nide 1.0 2 0.6 30 25 6.4 1.67 0.15 S-hexainothylsilazanylo 2. 0 1.0 0.6 30 25 3.6 0.26

l Ethyl aluminum sesquichloride. I Vanadium oxychloride. 3 Intrinsic viscosity.

Polymers having amines directly incorporated were is carried out at about 77 F. for 20 mins. in a sonic oscilprepared in a continuous manner as follows. lator.

TABLE II Nitrogen M lllimoles Shear loss, containing Time, Temp., Yield, Percent V percent Ex. No millimoles EASC VOCl; min. C. grams N SUS AV so 32s 69 10s as 1, 000 0. 13 54. s 4 56 312 61 102 as 1, 000 0. 07 61. 2 5 56 29s 60 110 as 1, 000 0. 01 so. 9 4

Example XIII The following example demonstrates an alternative route to the preparation of the compounds of this inven- Into a reaction vessel was introduced 5 gallons of benzene and 20 g. of 1-(2-aminoethyl)-2-(8-[9-decenyl])- irnidazoline and the mixture heated to 102 F. Solutions were prepared in benzene, one having 25% ethyl alumi' num sesquichloride and the other 6.905 weight percent vanadium oxychloride. A sufficient amount of the ethyl aluminum sesquichloride was added to the benzene solution to complex the amine containing monomer and the vessel pressured with propylene. Then, the vanadium oxychloride solution was added at a rate of 88 g. per hour, the ethyl aluminum sesquichloride solution was added at a rate of 125 g. per hour and a :50 mixture of ethylene/ propylene gas was added at a rate so that over a 1 hour and 14 minute period 1,000 g. of the gas mixture was added. During the run, the pressure ranged from about 9.1 to 11.3 p.s.i. The total amount of vanadium oxychloride solution added was 185 g., while the total amount of ethyl aluminum sesquichloride solution added was 335 g. The product was precipitated with a methanolic HCl solution and twice extracted with acetone. The polymer was then isolated by filtration and dried. Analysis: Wt. percent N, 0.101; viscosity at 210" F., 94.3 Saybolt Universal Seconds (SUS) (2.8 wt. percent in 130 neutral oil).

Following the procedure described above, a number of polymers were prepared having differing nitrogen contents and using as the basic nitrogen containing monomer 1-(2-aminoethyl)-2(8-[9-decenyl] )imidazoline. However, the results reported are for the polymer prior to extraction.

Also reported in the table are the viscosities at 210 F. in SUS (2.8 wt. percent in 130 neutral oil) and the shear. An extremely severe shear test is used: the degree of oscillation necessary to reduce a commercially available polyisobutylene thickener (Paratone N supplied by Enjay Chemical Co.) by 29% (Vis v /Vis -V um x 100) is determined and the same severity used with tion. In this example, a terpolymer of ethylene, propylene and 8-bromooctene-1 is first prepared, and then the bromine displaced with various amines.

Example XVII (A) Into a reaction flask was introduced 300 ml. of dry n-heptane, 0.83 g. of ethyl aluminum sesquichloride, 0.24 g. of pyridine, 1.0 g. of 8-bromooctene-l and 0.52 g. of vanadium oxychloride and the flask flushed with nitrogen. Into the resulting solution at room temperature was then introduced ethylene at a flow rate of 600 ml. per minute, propylene at a flow rate of 1,400 ml. per minute, hydrogen at a fiow rate of 13 ml. per minute and the flow maintained for 30 minutes. At the end of this time the catalyst was quenched with isopropanolic hydrochloric acid, and the polymer precipitated into methanol, washed with methanolic hydrochloric acid, methanol, followed by acetone and dried in a vacuum oven at C. for 12 hours. The yield was 11.8 g. Analysis: Wt. percent Br=2.17; intrinsic viscosity (Tetralin at 135 C.):0.9l5 dl./g.

(B) Into a flask was introduced 150 g. of polymer (prepared as described above) containing 0.81 weight percent bromine dissolved in benzene, 1.5 g. of 50 weight percent aqueous sodium hydroxide and 24.3 g. of Z-aminocthylpiperazine. The temperature was raised to C. while distilling olf the benzene and adding chlorobenzene. The reaction was maintained at 120 C. for 20 hours. The polymer was then precipitated into methanol, washed with methanol and acetone and dried. The yield was g. Analysis: Wt. percent N=0.33, 0.31; wt. percent Br: 0.085; viscosity index=133.

Following the above procedure using polymers having varying amounts of bromine, various amines were used to substitute the bromines to provide a variety of polymers within the purview of this invention.

TABLE 111 Weight percent Br Weight Temp., Time, Ex. No. Amine Before After percerrrrt Pressure 0. hr.

XVIII Dimethyl amine 2.8 XIX Di-u-gropyl amine 1.8 XX Di(2- ydroxyethyl)amtne. 2.6 XXL.v Trlethylene tetrumlne- 2. 6 1. XXIL. -do XXIII. do XXIV. N-[2nmlnoethyl)piperazln XXV" Triethylene tetramme. 0. 66

XXVII- Morphollne XXVIIL. Diethylene triamine XXIX ..do

The polymers of Examples XXVII and XXVIII were tested for shear stability according to the test previously described. The following are the results.

Shear loss,

Example: percent AV XXVII 7 XXVIII 2 The compounds of this invention can be used with various base oils which find use as lubricating oils, such as the naturally occurring naphthenic base, paraffin base, asphaltic base and mixed base petroleum lubricating oils. Synthetic lubricants include alkylene polymers, such as polymers of propylene, butylene, etc.; alkylene oxide type polymers and derivatives, dicarboxylic acid esters, such as octyl adipate, isooctyl azelate, hexyl alkenylsuccinate, etc.; and inorganic esters such as phosphates and silicates.

The above base oils may be used individually or in combination whenever miscible or made so by the use of mutual solvents.

The compositions of this invention can be used in oils of lubricating viscosity in amounts of from about 0.1 to 80 weight percent, depending on the use of the composition. When concentrates are to be used, prior to use in the engine, the amount will vary from about 10 to 80 weight percent. When the oil is to be used in an engine, usually the amount of the additive will be in the range of about 0.1 to 10 weight percent, more usually 0.25 to 5 weight percent. Concentrates are possible because of the excellent compatibility of the compositions of this invention with the various base oils.

In order to demonstrate the use of the compositions of this invention as viscosity index improvers, a number of the polymers were tested in a 130 neutral oil, for the most part at 2.8 weight percent, the Saybolt viscosity being determined both at 100 F. and 210 F. and the viscosity index determined therefrom. The following table indicates the results.

TABLE IV Polymer Ex. No.

2.5 weight percent in 130 neutral oil.

It is evident from the above results, that the polymers of this invention enhance the viscosity index of lubricating oils.

In order to demonstrate the effectiveness of the compositions of this invention as detergents in engines, a number of the compositions were tested according to a modified standard FL-Z test procedure as described in the June 21, 1948 report of the Coordinating Research Council. A standard procedure requires the maintenance of a jacket temperature of 95 F. and a crankcase oil temperature of 155 F. at 2,500 rpm. and 45 brake test, the engine is dismantled and the amount of sludge (rating of 0 to 50, no sludge being 50) and varnish (rated in the same way) is determined. Also determined is ring clogging reported as percent ring clogging.

The above test is modified by carrying out the test while periodically raising the oil sump temperature from 165 to 205 F. and the water jacket temperature from to 170 F. The oil sample used is a Mid-Continent base oil SAE 30 containing 2.5 weight percent of the candidate detergent and 15 mm./kg. of zinc 0,0-di(alkyl) phosphorodithioate (alkyl of from 4 to 6 carbon atoms). The following table indicates the results obtained.

TABLE V Total Total Percent ring varnish sludge clogging It is evident from the above results that the compositions of this invention provide excellent varnish and sludge control under the severe conditions of the test, which approximate the conditions of normal everyday automobile driving.

A number of the compositions of this invention were compounded in lubricating oils using the usual formulation, except that the compositions of the invention replaced the usual detergent. The compositions showed excellent detergency and maintained their performance over long periods of time.

To further demonstrate the effectiveness of the compositions of this invention as dispersants, a bench test was used described by C. B. Biswell et al., Ind. Eng. Chem. 47 1958, 1601 (1955). A solution was prepared by using 10 g. of a 2.8 weight percent solution of the candidate dispersant in 130 neutral oil and diluting this with 70 ml. of pearl oil. To this was added in a Waring Blendor 3 g. of a 20 weight percent slurry of carbon black in mineral oil. After blending for 3 minutes, the mixture was immediately poured into a 50 ml. stoppered graduate.

An inspection was made by periodically noting the level to which the carbon black had settled using a bright lamp. The results are reported as percent; is no discernible settling.

Example XXV Example XXVII 98%, 21 days 90%, 21 days The test demonstrates the excellent detersive capability of the compounds of this invention in retaining carbon black suspended in a hydrocarbon medium.

Of particular value are the polymers having from 0.06 to 1.0 weight percent nitrogen, wherein the nitrogen is obtained from alkylene polyamines (including piperazines).

A preferred aspect of this invention employs zinc 0,0 dihydrocarbyl phosphorodithioates in the engine oil with the detergents of this invention. The hydrocarbyl groups are of from 4 to 36 carbon atoms and about 1 to 50 mm./kg. of the dithiophosphate is used. Preferably, the hydrocarbyl groups are alkyl or alkaryl.

It is evident that the compounds of this invention not only provide viscosity index improvement in lubricating oils but also neutralize acids formed from the oxidation of the lubricating oil and maintain products dispersed in the oil which otherwise form sludge and varnish deposits and clog rings.

As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

I claim:

1. A hydrocarbonaceous oil soluble random terpolymer having an intrinsic viscosity of from about 0.2 to 1.5 dl./ g. and from about 0.05 to 2 weight percent basic nitrogen, wherein two of the olefins of said terpolymer are aliphatic l-olefins of from 2 to 6 carbon atoms which are each individually present in at least 30 mole percent, the total mole percent of said 2 olefins is in the range of 95 to 99.95, and the third olefin is a basic nitrogen containing olefin which is present in form about 0.05 to 5 mole percent and is of the formula:

X is an alkylene group of from 1 to carbon atoms;

Y is a basic nitrogen containing radical, wherein the basic nitrogen is at least beta to the olefinic group, of from 0 to 16 carbon atoms, 1 to 6 basic nitrogen atoms, 0 to 2 silicon atoms, said silicon atoms being combined with amino groups to form silazane groups, and from 0 to 2 oxygen atoms, said oxygen atoms being present as hydroxyl or ethereal functional groups, and

wherein said terpolymer is prepared by polymerizing said olefins at a temperature in the range of 10 to 100 C. in an inert hydrocarbon diluent in the presence of a complex catalyst comprising vanadium oxychloride and an alkyl aluminum compound selected from the group consisting of alkyl aluminum sesquichloride, dialkyl aluminum chloride and trialkyl aluminum, wherein the alkyl groups are of from 1 to 3 carbon atoms,

wherein the ratio of aluminum to vanadium is in the range of 2 to 20 atoms of aluminum per atom of vanadium and there being from 0.1 to 1 mole of said amino containing olefin per atom of aluminum in the catalyst,

with the proviso that the hydrocarbon olefins are maintained in solution during the polymerization at a substantially constant mole ratio.

2. A terpolymer according to claim 1, wherein the mole percent of said basic nitrogen containing olefin is in the range of 0.1 to 3.

3. A terpolymer according to claim 1, wherein Y is:

and wherein T and T are the same or dilferent and are hydrogen, hydrocarbon radicals of from 1 to 12 carbon atoms, hydroxy or alkoxy hydrocarbon radicals of from 2 to 10 carbon atoms or trialkyl silyl radicals of from 3 to 12 carbon atoms.

4. A terpolymer according to claim 1, wherein Y is:

{NH( Z 1 131-111,

and wherein Z is alkylene of from 2 to 6 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms, and p is an integer from 1 to 5.

5. A terpolymer according to claim 1, wherein Y is wherein N and C have their ordinary meaning of nitrogen and carbon; A and D may be the same or diflerent and are nitrogen or oxygen; a, c and e are integers of from 0 to 3; b and d are integers of from 0 to 1; the sum of a, b, c, d and e is in the range of 4 to 5, the total number of carbon atoms being not greater than 16, there being from 0 to 3 alternating double bonds in the ring, and the remaining unsatisfied valences of A and D, when they are nitrogen, and the annular carbon atoms are satisfied by a member of the group consisting of hydrogen, lower alkyl and aminoalkyl of from 2 to 3 carbon atoms.

6. A terpolymer according to claim 1, wherein Y is cyano.

7. A terpolymer according to claim 1, wherein X is polymethylene of from 2 to 6 carbon atoms.

8. A terpolymer according to claim 1, wherein said aluminum alkyl is alkyl aluminum sesquichloride.

9. A terpolymer according to claim 1, wherein said hydrocarbon olefins are ethylene and propylene.

10. A terpolymer according to claim 9, wherein ethylene is present in from 45 to 60 mole percent and propylene is present in from 55 to 40 mole percent.

11. A lubricating oil composition comprising from 0.1 to weight percent of a hydrocarbonaceous oil soluble random terpolymer having an intrinsic viscosity of from about 0.2 to 1.5 dl./g. and from about 0.05 to 2 weight percent basic nitrogen, wherein 2 of the olefins of said terpolymer are aliphatic l-olefins of from 2 to 6 carbon atoms which are each individually present in at least 30 mole percent, the total mole percent of said 2 olefins is in the range of to 99.95, and the third olefin is a basic nitrogen containing olefin which is present in from about 0.05 to 5 mole percent and is of the formula:

wherein X is an alkylene group of from 1 to 10 carbon atoms;

Y is a basic nitrogen containing radical of from 0 to 16 carbon atoms, 1 to 6 basic nitrogen atoms, 0 to 2 silicon atoms, said silicon atoms being combined with amino groups to form silazane groups, and from 0 to 2 oxygen atoms, said oxygen atoms being present as hydroxyl or ethereal functional groups.

12. A lubricating oil composition according to claim 11 wherein said aliphatic olefins are ethylene and propylene.

13. A lubricating oil composition according to claim 12, wherein said ethylene is present in from 45 to 60 mole percent and propylene is present in from 55 to 40 mole percent.

14. A lubricating oil composition according to claim 11, wherein Y is:

and wherein T and T are the same or diiferent and are hydrogen, hydrocarbon radicals of from 1 to 12 carbon atoms, hydroxy or alkoxy hydrocarbon radicals of from 2 to 10 carbon atoms or trialkyl silyl radicals of from 3 to 12 carbon atoms.

15. A lubricating oil composition according to claim 11, wherein Y is of the formula:

{N11 ll l}: u and wherein Z is alkylene of from 2 to 6 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms, and p is an integer from 1 to 5.

16. A lubricating oil composition according to claim 11, wherein Y is of the formula:

ii u

-(.3QD4 wherein N and C have their ordinary meaning of nitrogen and carbon; A and D may be the same or different and are nitrogen or oxygen; a, c and e are integers of from to 3; b and d are integers of from 0 to 1, the sum of a, b, c, d and e is in the range of 4 to 5, the total number of carbon atoms being not greater than 16, there being References Cited UNITED STATES PATENTS 2,749,312 6/1956 Hollyday 252 2,838,456 6/1958 Banes et al. 25250 3,000,822 9/1961 Higgins et al.

3,092,563 6/1963 Agius et al 252 50- XR 3,125,462 3/1964 Rachinsky 26080.73 XR 3,293,326 12/1966 Jezl et a1 26080.73 XR 3,308,108 3/1967 Felclhofi et al. 2603S.1

PATRICK P. GARVIN, Primary Examiner.

US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,445,387 May 20, 1969 Thomas V. Liston It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 43, "is intended which" should read is intended nitrogen which Column 3, line 51, "the containing" should read the amine containing Column 5, line 31,

L "2 {minopyridine" should read Z-aminopyridine line 45 f"hy rocarbons" should read hydrocarbon lines 60 and 61, "'atoms", each occurrence, should read atom Column 6,

line 10, "of the olefins" should read of the olefin line 33, "amines" should read amine Column 8, TABLE I, the last column should appear as shgwn below:

Analysis Wt. N

OCDOQQOOOQOCD Column 7, TABLE II, the first heading following Ex. No., should appear as shown below:

Nitrogen Containing Monomer Millimoles Signed and sealed this 28th day of April 1970.

( E Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents