DE1594610B2 - LUBRICATING OIL PREPARATIONS - Google Patents

Description

N - (R'NH) "H

in which R 'is a divalent alkylene radical having 2 to 14 carbon atoms, R is a hydrogen atom or a hydrocarbon radical having 1 to 30 carbon atoms and π is a number with the value from 1 to about 10, in an amount from about 0.3 to 1 mole of RCOOR 'in component (A).
2. lubricating oil preparation according to claim 1, characterized

characterized in that it is a polyamine of the general formula as component (B)

45 R

N - (R'NH) "H

where R 'is a divalent alkylene radical having 2 to 7 carbon atoms, R is a hydrogen atom or an alkyl radical having 1 to 7 carbon atoms and η is a number from 2 to 6, in an amount of 0.8 to 1 mol per mol of RCOOR' in the component (A) contains.

3. lubricating oil preparation according to claim 1 or 2, characterized in that it is used as component (B) a polyamine of the general formula

N - (R'NH) "H

means divalent alkylene radical with two carbon atoms.

4. Lubricating oil preparation according to claims 1 to 3, characterized in that it is used as component (B) contains a tetraethylene pentamine, the molar ratio, based on RCOOR ', in component (A) is about 1: 1.

5. lubricating oil preparation according to claims 1 to 4, characterized in that it is used as component (A) contains an oil-soluble polymer which essentially consists of the general formula RCOOR ', where R an ethylenically unsaturated alkyl radical having 8 to 20 carbon atoms, and R 'is a hydrogen atom or a lower alkyl radical is 5 to 25 mole percent of a conjugated, diethylenically unsaturated aliphatic hydrocarbon having 4 to 5 carbon atoms, and 85 to 50 moles of one normal α-monoalkene with 12 to 21 carbon atoms consists.

6. lubricating oil preparation according to claims 1 to 5, characterized in that it is used as a compound of general formula. RCOOR 'contains a methyl oleate.

7. Lubricating oil preparation according to claims 1 to 6, characterized in that it is used as diethylenic contains unsaturated aliphatic hydrocarbon 1,3-butadiene.

8. lubricating oil preparation according to claims 1 to 7, characterized in that it is a base oil contains mineral lubricating oil.

contains where R is hydrogen and R 'is a number of those currently on the market Passenger cars are mainly used for short journeys (rush hour traffic). This is done here Driving with frequent stops, which prevents the automobile from warming up completely or being used given is. In this way, the motors are loaded little and not operated continuously, so that they barely get warm enough to work efficiently. The one in such engines Fuel used Petrol is known as an easily combustible fuel. Gasoline burns easily when the combustion chamber of the engine reaches a sufficiently high temperature and the fuel evaporated in the same and mixed with sufficient oxygen. At a Such combustion burns the gasoline completely, and only harmless carbon dioxide gas is formed and water vapor. However, the engine does not work long enough to keep its coolant and crankcase heat to at least 60 ° C, so some carbon dioxide and water vapor escapes through the Piston rings, condenses in the cold crankcase and forms liquid carbonic acid, which iron and steel for Rust brings.

If the engine is cold and it is operated at the low speeds typical for short trips, then it is the combustion insufficient and incomplete. Under these conditions the gasoline is only partially consumed burned, and a lot of carbon, gaseous carbon monoxide, partially oxidized gasoline is formed, and highly corrosive fuel acids in the combustion chambers (in addition to the usual carbon dioxide gas and water), which escape through the piston rings and the crankcase oil

contaminate. The material resulting from incomplete gasoline combustion causes numerous Engine damage and often costly damage when it collects in the crankcase. Such harm are z. B. seized and defective hydraulic valve lifters. worn cams of the cam disc, stuck Piston rings, high piston ring and cylinder wear with correspondingly high oil consumption and Oil pollution; Corroded bearings, damaged pistons, clogged oil pump screens, which can lead to interruption ι ο the engine oil supply can result in burned bearings and seized pistons. A modern lubricating oil must therefore prevent the build-up of solid products on the engine surfaces that normally come with the lubricant come into contact, prevent.

Another source of the difficulties arising from deposits in internal combustion engines are the additives usually incorporated into the lubricants, in particular the metal-containing additives such as z. B. the organic, metal-containing salts that are incorporated into the oil to increase its cleaning power. If the oil in the engine is burned (the oil present in the cylinder wall is burned) Oil film during the piston stroke), then all metal-containing additives present in the oil can form ash, which partially deposit on the various surfaces of the combustion chamber, spark plugs and valves. The aim of the present invention is therefore to develop a lubricating oil preparation that can be used with metal or mineral-free cleaning agents.

Another major supplier of engine deposits is the incompletely burned gasoline, in particular the metal additives contained in the fuel. Prevent the ashless cleaning agents according to the invention sludge formation in the engine and disperse any sludge that may have formed. Since many Years ago, the detergent additives that were mainly used successfully were organic, metal-containing ones Compounds such as calcium petroium sulfonate, calcium cetyl phosphate, Calcium octyl salicylate, calcium phenyl-4c stearate or the potassium salt of the reaction product of phosphorus pentasulfide and polybutene. Various of these Detergents work by chemically reacting with precursors to form harmless compounds. Others prevent the flocculation or coagulation of solid particles in oil and keep it in the state of one Suspension of finely divided particles. Other materials not only have this dispersing function, but they affect the solubilization or emulsification of the sparingly soluble monomers in the oil and reduce hence the rate of polymerization is essential. In the latter case, the polymerization materials which form within the oil are smaller in size and can be peptized or peptized in oil much more easily are dispersed than is the case with large polymer particles deposited on the exposed engine surfaces or be formed in drops within the oil. The detergent with a dispersing as well as solubilizing or emulsifying function are preferred whenever possible, especially in Motor vehicle engines intended to be driven in city traffic.

Although these metal-containing organic compounds are used as cleaning agents to disperse these Deposition precursors are effective, they have the disadvantage of building ash deposits in the engine.

About the problems of organic cleaning agents containing metal To circumvent this, non-metallic detergents have been developed. Sulphurized and phosphorus sulphurized, long-chain hydrocarbons have cleaning properties; put these detergents however, when heated, it releases hydrogen sulfide and forms 0.1 to 0.2% ash. A certain cleaning effect has been used in macromolecular compounds, mainly phenols and phenolic resins, established. Acrylate polymers have also been used, and some of the carboxyl function has been used long-chain, oleophilic alcohols and the remainder with hydrophilic polyglycol ethers esterified or amidized or neutralized with amines.

Many non-metallic detergents usually have a low basicity and therefore could the harmful effects of the sulfuric acid formed in situ in the oil are not effectively counteracted. To the To increase the basicity of cleaning agents, polyamine salts and amides were used as possible cleaning agents investigated (see for example US patent specification 30 18 247, in which such cleaning agents, such. the N-polyamine substituted monoalkanylsuccinimides).

In US-PS 3116 248 a lubricating oil additive is used described, which consists of a copolymer of a polymerizable heterocyclic amine, such as vinyl pyrrolidone or vinyl pyridine, and long chain alkyl acrylates or alkyl methacrylates with molecular weights from 100,000 to 850,000, and further consists of an oil-soluble Ce-Cie alkylguanidine salt.

From GB-PS 8 54 658 a lubricating oil additive is known which is an oil-soluble polymer or copolymer of a Amine ester of the formula

R ³

R ²

NC-COOR ⁵

R ¹ -C COOR ⁴

where R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} hydrogen or alkyl, but at least one of the substituents R ⁴ or R ^{5 is} alkyl.

The above polymers are all materials made from monomers with α, / 3 double bonds to give carboxylic acid groups using free radicals producing, p ^ coxidic catalysts will. While Friedel-Crafts polymerizations are normally carried out at room temperature, radical polymerizations can only be carried out at much higher temperatures. The former can can therefore be regulated much more economically.

The object of the present invention is to develop a lubricating oil preparation containing the above Avoids disadvantages of known lubricating oil preparations. In particular, it should be cleaning agents (detergents) that result in ashless combustion products.

The invention now relates to a lubricating oil preparation consisting of a larger proportion of a Base oil with lubricating viscosity and a lower proportion of an oil-soluble condensation reaction product the end

(A) an oil-soluble polymer containing a) about 3 to 55 mol percent of a compound of the general Formula RCOOR ', in which R stands for an ethylenically unsaturated hydrocarbon radical with 2 to 25

iö 94

Carbon atoms, R 'stands for a hydrogen atom or an alkyl radical with 1 to 15 carbon atoms, and the COOR' group is bonded to an aliphatic carbon-carbon chain with at least 2 carbon atoms of the group R s, b) about 5 to 30 mol percent of a conjugated, diethylenically unsaturated, aliphatic hydrocarbon having 4 to 12 carbon atoms and c) about 92 to 15 mol percent of an α-monoalkene having 3 to 25 carbon atoms, the RCOOR 'and the α-monoalkene being chosen so that the total number of carbon atoms in these components is at least is about 12, and
(B) a polyamine of the general formula

N - (RZNH) _n H

20th

in which R 'is a divalent alkylene radical having 2 to 14 carbon atoms, R is a hydrogen atom or a hydrocarbon radical having 1 to 30 carbon atoms and η is a number with the value from 1 to about 10, in an amount from about 0.3 to 1 mole per mole of RCOOR'in component (A).

In a preferred embodiment, the cleaning agents added according to the invention consist of Invention from about 10 to 25 mol percent of the olefinically unsaturated carboxylic acid or its ester, about 5 to 25 mole percent of the conjugated diolefinically unsaturated aliphatic hydrocarbon, about 50 to 85 Mol percent of the α-olefin and the stated proportion of organic amines.

The unsaturated acids or esters that form the new, basic, oil-soluble extreme pressure additive which can be polymerized with the α-olefins and dienes are acids or esters of the formula R — COOR ', in which R stands for an unsaturated hydrocarbon radical having 2 to 25 carbon atoms, preferably 8 to 20 carbon atoms. The group R contains one or more, preferably 1 to 2, olefinic Ties and can e.g. B. be substituted with acetylenic, aromatic groups, etc., provided that the carboxyl group (-COOR ') on an aliphatic, including cycloaliphatic, carbon-carbon chain is bonded with at least 2, preferably at least 8 carbon atoms. R is preferably for an unsaturated alkyl radical. R 'represents a hydrogen atom or an alkyl group of 1 to 15 Carbon atoms, preferably a lower alkyl group of about 1 to 3 carbon atoms. If R 'for Is alkyl, the salt formation of the acid with the catalyst used for the polymerization is prevented, and the alcohol formed later in the reaction with an organic amine can often easily be distilled off from the product. The acids which can be used in the polymer according to the invention are, for. B. Oleic acid, linoleic acid, undecylenic acid. Linolenic Acid, Castoroleic Acid, Methachrylic Acid, etc. It can also the lower alkyl esters of these acids including the glycerides, especially the methyl esters, are used will.

The -olefins or -monoalkenes can be replaced by the

general formula

R '-CH-CH = CH ₂
R "

in which R 'and R "each represent a hydrogen atom or an alkyl group, inclusive Cycloalkyl group, the total number of carbon atoms between about 3 and 25, preferably about 12 and 21. Expediently, one of the groups R 'and R "represents a hydrogen atom and the others for a straight chain alkyl group to give an n-olefin. The «olefins are often called Mixture is used and can be small amounts, i. H. usually less than 10 weight percent, others Hydrocarbons such as other olefins, diolefins, saturated hydrocarbons and aromatics.

The conjugated, diethylenically or diolefinically unsaturated, aliphatic used in the polymer Hydrocarbons comprise the polymerizable

ren conjugated, diethylenically unsaturated alkenes with 4 to 12 carbon atoms, preferably 4 to 5 Carbon atoms such as B. conjugated diolefins with a terminal double bond, such as 1,3-butadiene, Isoprene, etc. The diolefin may be substituted with, for example, halogen atoms, etc. so long as the substituent has the Does not interfere with polymerization or has any other adverse effect. A substituted, conjugated Diolefin is e.g. B. chloroprene.

The choice of the unsaturated acid, the conjugated, diethylenically unsaturated, aliphatic hydrocarbon and α-olefins, their proportions and the degree of conversion are carried out so that an oil-soluble Polymer obtained; usually the total number of carbon atoms in the acid and in the α-monoolefin at least about 12, preferably at least about 18. To produce a given polymer, you can also more than one acid, more than one conjugated, diethylenically unsaturated, aliphatic hydrocarbon or more than one -olefin can be used, and small amounts of other polymerizable Monomers be present. v

The polymer can be prepared by adding the α-olefin, the diethylenically unsaturated, conjugated, aliphatic. Hydrocarbon and the unsaturated acid or the ester to a polymerization ^{temperature of about 0 to 50 0} C, preferably about 0 to 25 ° C, in the presence of a strong Friedel-Crafts catalyst, such as aluminum chloride or boron trifluoride, subjected. A preferred catalyst is aluminum chloride; it is advantageous to add the unsaturated acid and the conjugated, diethylenically unsaturated aliphatic hydrocarbon to the α-olefin. A catalyst can also be used, usually present in an amount of from about 0.5 to 5 volumes per volume of the acid, alpha-olefin, and diene charge. Corresponding cocatalysts are the lower alkyl halides, especially ethyl chloride, methyl chloride, etc.

In the catalyst solution. is generally the strong Friedel-Crafts catalyst in one concentration from about 0.5 to 15 percent by weight, preferably about 2 to 7 percent by weight, present; the used The amount of Friedel-Crafts catalyst is usually from about 0.1 to 20 percent by weight, preferably

about 2 to 15 percent by weight of the polymer formed over any polymer present Percentage of the catalyst that reacts with the carboxyl group of the acid. The proportions of conjugated, Diethylenically unsaturated alkene, unsaturated acid and -olefin for the catalyst solution can between about 1: 2 and 1: 10, even about 1: 4 to 1: 5 moles of Reactants are per mole of catalyst solution. When the acid form is reacted, so will usually at least 0.5 moles of catalyst per mole of acid are used in the reaction mixture. That Polymer can by simultaneous addition of the catalyst solution and the mixture of unsaturated Acid, conjugated, diethylenically unsaturated alkene and -olefin are formed to the reaction vessel. That volumetric ratio of the catalyst solution to the reactants in a given unit of time is often about 2: 1 to about 4: 1, preferably about 3: 1.

When the addition of catalyst and reactants has ended, the polymerization is allowed to take place persist for a short time, d. H. generally about 5 to 45 minutes for the polymerization to become oil soluble Polymer, e.g. B. a normally liquid material with a kinematic viscosity of about 25 to 1000 centistokes at 99 ° C, preferably about 30 to 150 or up to about 300 centistokes. The polymerization can then be carried out using a lower alkanol, ζ. B. having 1 to 4 carbon atoms, terminated in solution in a lower alkane will. The polymer obtained can from the remaining catalyst z. B. by washing with water, alcohol, separated from dilute sodium hydroxide solution, hydrochloric acid or other suitable hydrolysis and washing processes will.

The ashless detergent is produced by condensation of the polymer from oc-olefin, conjugated, diethylenically unsaturated alkene and unsaturated acid with a practically aliphatic polyamine manufactured. Suitable polyamines can be represented by the general formula

N (R'NH) "H

are represented, in which R 'stands for a divalent alkylene radical with 2 to 14 or more carbon atoms, preferably 2 to about 7 carbon atoms; R stands for a hydrogen atom or hydrocarbon radicals, such as alkyl radicals including cycloalkyl radicals, e.g. 1 to 30 or more carbon atoms, preferably have 1 to about 7 carbon atoms; π is a number with a value from 1 to 10, preferably about 2 to 6.

R 'can be between two nitrogen atoms, e.g. B. between the two N atoms which R 'is bonded, and in this case those nitrogen atoms have only one more free bond. the Substituents R and R 'can be unsaturated, but are preferably saturated; they can't go through interfering substituents, especially lower alkyl groups, be substituted. So only imidazoline formation a 1,2-diamine can be used, one of which Amine group is primary; suitable amines can be represented by the general formula

H R 'R' H

\ I I /

N — C — C — N

/ I I \

R R 'R' H

are represented, wherein R as above is a hydrogen atom or an alkyl group, preferably a Is an aminoalkyl group having 1 to 30, preferably 1 to about 7 carbon atoms; R 'stands for a Hydrogen atom or an alkyl group having 2 to 14 or more carbon atoms, especially 2 to about Carbon atoms. R can also be a hydroxyalkyl, alkoxyalkyl or aromatic radical.

The polyamines include monoalkylenediamines, dialkylaminoalkylamines and the polyalkylene polyamines. Suitable monoalkylenediamines are, for. B. Ethylenediamine, Propylenediamine, butylenediamine, octylenediamine, etc. Suitable dialkylaminoalkylamines are e.g. B.

Dimethylaminoethylamine,
Dimethylaminopropylamine,
Dimethylaminobutylamine,
Diethylaminopropylamine, diethylaminoamylamine, dipropylaminopropylamine,

Methylpropylaminoamylamine,
Propylbutylaminoäthylamin etc. Suitable polyalkylenepolyamines are, for. B. Diethylenetriamine, Triäthylenetetramin.Tetraäthylenpentamin, Hexapropylenheptamin, Tetrabutylenpentamin, Polyamin D [a mixture of aliphatic and cyclic Polyäthyleneamines with a boiling point over 340 ° C and a similar average molecular weight as Pentaäthylenhexamin, which as main components, as main components diaminoäthylenetetrisches, symmetrical diaminoäthylenhexamine, symmetrical diaminoäthylenhexamine, symmetrical and unsymmetrical diaminoäthylenhexamine and asymmetrical diaminoethyl, diaminoethylpiperazine,

Piperazinoäthyltriäthylenetetramine, 4- (N-piperazrnaäthyl) -triethylenetetramine, bis-piperazinoäthylamine and
Aminoethyl- (dipiperazinoethane) contains], polyamine H (bottom products from the production of tetraethylene pentamine) etc. Suitable N- (j3-aminoalkyl) -piperazines are N-methyl-N '- (j9-aminoethyl) -piperazine, N- (j3- Aminoisopropyl) piperazine etc.

When converting the polymer from an unsaturated acid or an ester, the conjugated, Diethylenically unsaturated alkene and α-olefin with an organic polyamine to produce the As a detergent, the polyamine is usually used in a mole ratio of about 0.3 to 1 mole per mole unsaturated acid or ester implemented in the polymer. The molar ratio is preferably between 0.8 and 1: 1, especially around 1: 1. The ratio of the polyamine to the polymer can also in gram atoms of hydrogen-bonded nitrogen in the polyamine per molar equivalent of carboxyl groups expressed in the polymer. In

609 519/379

Considering the polyamine of the general formula
R.

N (R'NH) "H

a molar ratio of 0.3: 1, preferably 0.8: 1, of the polyamine per mole of the acid or ester in the polymer is equivalent to 0.3 to 11, preferably 0.8 to 11 gram atoms of hydrogen-bonded nitrogen per molar equivalent of Carboxyl groups in the polymer. The lower limit values are obtained when / 7 = 1 and both R radicals denote hydrocarbon radicals. The upper limit value is obtained when η = 10 and at least one R is hydrogen. A slight excess of amine is advantageous in order to ensure practically complete conversion of the acyl group of the polymer and to avoid unnecessary crosslinking; possibly even a large excess of amine can be present. The reaction is usually carried out at a temperature of about 60 to 32O ⁰ C. The temperature depends on whether an amide or imidazoline is desired. The reaction temperature for amide formation is about 80 to 150 ^° C. and for imidazoline formation about 250 to 300 ^° C. The reaction is carried out in such a way that an oil-soluble base product is obtained; it often takes about 0.25 to 5 hours, preferably about 0.5 to 3 hours; water or alcohol is removed as it is formed. The polymer obtained is basically oil-soluble and usually has a kinematic viscosity of about 1000 to about 20,000, preferably about 3000 to 15,000 centistokes at 38 ° C. and a kinematic viscosity of at least about 50 to 1000, preferably about 150 to 750 centistokes at 99 ° C. The detergent additives are added to the lubricating oils in small, effective amounts, usually between about 0.1 and 10 percent by weight or more, preferably about 0.25 and 7.5 percent by weight, based on the oil.

Those which can be used as the base oil or main component of the lubricating oil preparations according to the invention Lubricating oils include many oils with lubricating viscosities, such as. B. naphthenic, paraffinic and mixed Mineral base oils; other hydrocarbon lubricants, e.g. B. Lubricating oils derived from coal products are derived; and synthetic oils, e.g. B. alkylene polymers, such as B. Polymers of propylene, butylene, etc. and mixtures thereof; Alkylene oxide polymers (e.g. alkyleneoxy polymers obtained by polymerizing the alkylene oxide, e.g. propylene oxide, etc. in Presence of water or alcohols, e.g. B. Ethylene alcohol, are produced), carboxylic acid esters (e.g. those by esterification of dicarboxylic acids such as adipic acid, azelaic acid, suberic acid, sebacic acid, Alkyl succinic acid, fumaric acid, maleic acid etc., with alcohols such as butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, Dodecyl alcohol, etc.). The above base oils can be used individually or in combination can be used if they are miscible with each other or by using common solvents can be made mixable.

The synthetic oils to which the polymeric reaction products can be added include synthetic ester-based oils having lubricating viscosities consisting essentially of carbon, hydrogen and oxygen, e.g. B. Di-2-ethylhexyl sebacate. Many of these lubricating materials are known, and their viscosity ranging from mild to heavy oils, for example about 50 SUS at 38 ⁰ C to 250 SUS at 99 ⁰ C., preferably 30 to 150 SUS at 99 ° C. These esters have improved heat resistance, a lower acid number, and high flash and fire points. The complex esters, diesters, and monoesters

ίο polyesters can be used alone; to the Complex esters, diesters, and polyesters can be used to achieve the most convenient viscosity properties with each other or with naturally occurring esters such as castor oil. Lubricants are obtained whose wide viscosity ranges can be precisely matched to the various uses. This mixing is done e.g. B “by adding a given amount of diester and complex ester at increased Temperature, changing the proportion of each component until the desired one Viscosity is reached. The ones used to make the synthetic ester base stocks Mono- and dicarboxylic acids can be branched or straight-chain and saturated or unsaturated and often contain about 2 to 12 carbon atoms. The alcohols usually contain about 4 to 12 carbons Atoms of matter. Suitable glycols are generally the aliphatic monoglycols with 4 to 20 or 30 Carbon atoms, preferably 4 to 12 carbon atoms.

Materials commonly found in lubricating oils can be added to the preparation of the present invention can be used to confer special properties. These include corrosion inhibitors, extreme pressure agents, anti-wear agents, etc. The amount of such additives used in the preparation is usually between about 0.01 and 20 weight percent or more; in general they can be in any desired amount can be used as long as the preparation is not adversely affected.

The following examples illustrate the present invention.

example 1

To a mixture of α-olefins with about the following composition:

Weight percent Total olefins 95 + Total α-olefins 94 Straight chain α-olefins 86 Branched and naphthenic Olefins 3 Straight-chain, ω-diolefins 6th Saturated and aromatic Hydrocarbons 4th

Molecular weight distribution,
Number of carbon atoms

Weight percent

14th
15th
16
17th
18th
19th
20th
21

12th 19th 18th !8th 17th 14th

were isoprene and linoleic acid in a molar ratio of α-olefin to isoprene to linoleic acid of 6.65 / 2.45 / 1.0 based on the average molecular weight (243) of the oc-olefin mixture was added. A One liter flask was fitted with a Dean-Stark trap and two addition funnels. The Dean Stark trap a dry ice trap was placed to remove the volatile solvent used in the polymerization Remove ethyl chloride and condense. A funnel with olefin / linoleic acid / diethylenically unsaturated Alken charged, in the other funnel was a catalyst solution of 5.2 g of aluminum chloride per 100 ecm of ethyl chloride given at 12 ° C.

The charge of the reactants and the catalyst solution were introduced simultaneously into the reaction flask, namely the mixture of olefin, linoleic acid and diethylenically unsaturated alkene at a rate of 24.2 ecm per minute (0.0615 mol per minute Ci ₄ -C ₂ ] « -Olefin, 0.026 mole per mole isoprene and 0.00923 mole per minute linoleic acid) and the catalyst solution at a rate of 49 cc / min (0.0192 mole / min aluminum chloride). The total addition time was 10 minutes, then the polymerization mixture was stirred for an additional 20 minutes. The temperature during the polymerization was 16 ⁰ C, and there were 320 cc (61%) of ethyl chloride by means of the case from the polymerization station. To quench the catalyst, 400 ecm hexane and 400 ecm isopropanol were added.

The polymerization was washed with dilute hydrochloric acid and a further 3 times with water. It was by Freed solvents and had a KV (kinematic viscosity) of 3603 cP at 38 ° C and a KV of 199.54 199.54 cps at 99 ° C; Acid number = 25.44; Iodine number = 43.9; spec. Weight = 0.8778.

100 g of des given above polymer and 8.0 g of tetraethylene pentamine; the system was up within 15 minutes flushed with nitrogen, the temperature being increased to 65 ° C. Within 20 minutes it was the temperature increased to 270 ° C; 75 minutes at 270 ° C. were used for easier water removal Vacuum of 15 cm applied. Under this reduced pressure, the temperature became room temperature let sink. The product was washed and the solvents removed. The polymer had a spec. Weight = 0.8933; (KV 13 50OcP at 38 ° C; KV 550.63 cP at 99 ° C; iodine number = 47.4 and 2.51 Nitrogen). The C = N bond and the imidazoline ring structure were determined by infrared analysis confirmed a trace of amide present. The polymer was used as an ashless cleaning agent in a neutral 95 V.I. Mid-Continent oil in the detergency bench test described in US Pat. No. 3,044,860 tested at low temperature. The results were as follows:

20 base oil

Base oil + 2% additives

Example 2

Rating (100 = clean)

22 87

The same reaction apparatus as in Example 1 was used. 1,3-Butadiene and methyl oleate were added to a mixture of the -olefin charge according to Example 1 in a molar ratio of methyl oleate to butadiene to -olefin of 1: 3: 4, based on the average molecular weight of the -olefin mixture. In a feed vessel, the olefin / methyl oleate / butadiene was introduced feed and a catalyst solution of 5.2 g of aluminum chloride per 100ecm ethyl chloride at 12 ⁰ C in the other vessel. The olefin / acid feed and the catalyst solution were simultaneously introduced into the reaction flask, the olefin / acid feed at a rate of 19.6 cc / min and the catalyst solution at a rate of 49.4 cc / min. The total addition time was 12 minutes; then the polymerization mixture was stirred for an additional 12 minutes. The temperature during the polymerization was 15.5 ° C; 340 ecm of ethyl chloride (57.5%) were removed from the system using a trap. The catalyst was quenched with 400 ecm hexane and 400 ecm isopropanol. The polymer was washed with water and freed from solvents. It had a saponification number of 38.0 (specific weight = 0.8897; iodine number 32.0; KV 1317.0 cP at 38 ° C.).

26 g of tetraethylene pentamine were added at 26 ° C. to 200 g of the polymer. The system was flushed through with nitrogen and the temperature was increased ^{to 270 ° C. within 50 minutes.} A vacuum of 19 cm was applied for an additional 90 minutes. The reaction product was allowed to cool to room temperature under this reduced pressure. The nitrogen analysis showed a nitrogen content of 3.69%. '"""-

The additive was tested in the C.L.N. oil test engine at 1% concentration using the »Engine Car Manufacturer's Sequence SA for Motor OiIa for Service MS «method tested. The details of the Procedures are given in Table 1 below.

Table 1

Duration of experiment: 240 hours; no oil filter; no oil change; Oil charge: 0.95 1; Oil added as needed; Fuel: Certified MS 08: after 61 ³ A, 125 ³ A and 189 ³ A hours, samples of 56 g are taken.

time in
Hours.

Revolutions
per minute

Approximate torque in mkg Ignition advance in
Degree

Ratio off
air and
fuel

Approximate charge in kg per hour of fuel air

0.75 550-650 idle = 0.0277

2 1790-1810 operation = 0.4839-0.6913

9.5-10.5
15.5-16.5

0.272-0.318 1.81

2.72-3.18 31.8

continuation 90.5-96
35-40.5 13th 15 94 6 10 14th Temperature below
differentiated between
Water ingress and
Water outlet in "C Phase temperature of
Mix in ⁰ C Blow-through
speed
in m ^J per hour Exit
temperature of the
Water in ⁰ C Temperature of
Oil over that
Crankcase
in ⁰ C Approximately
oil pressure
in kg / cm ² 0.5-1.1
2.2-2.8 1
2 High performance 50.5-55
50.5-55 38-52
71-77 1.41
2.81

The cycle was repeated 5 times (13 ³ Å hours in total). The engine was stopped and water was circulated at 95 to 97 ° C for 2> A hours (16 hours total). The engine was allowed to cool to room temperature over 2 hours. This entire cycle was repeated 15 times for a total of 240 hours.

The results are given in Table 2.

Table 2

reason Basic mix mixture + 1% addition middle Time to the start of 96 224 Deposits; Hours. Final evaluation 24.9 45.8 after 240 hours (50 to 100% clean)

Example 3

The same reaction apparatus as in Example 1 was used. To a mixture of the α-olefin charge according to Example 1, isoprene and methyl oleate were added to a molar ratio of α-olefin / isoprene to methyl oleate of 6.05: 2.05: 1.00, based on the average molecular weight of the α-olefin mixture, admitted. The polymerization apparatus was the same as in Example 1. One funnel was charged with the reactants and the other with a catalyst solution of 5.2 g of aluminum chloride per 100 ecm of ethyl chloride. The olefin feed and catalyst solution were simultaneously introduced into the reaction flask with the olefin mixture at a rate of 20.8 cem / min (0.0525 mole / min alpha-olefin, 0.0173 mole / min isoprene, 0.00860 mole / min. min methyl oleate) and the catalyst solution at a rate of 39.5 cem / min (0.0154 mol / min aluminum chloride). The total addition time was 12 minutes; the polymerization was continued for an additional 28 minutes. The polymerization temperature was 16 ° C., and 280 ecm (59%) of ethyl chloride were removed from the polymerization system by means of a trap. To quench the catalyst, 400 ecm hexane and 400 ecm isopropanol were added. The polymer was washed with water and after removal of the solvent had the following properties: KV @ 38 C = ⁰ 119OcP; KV at 99 ° C = 94.54 cP; Iodine number = 30.7; Saponification number = 24.3; spec. Weight = 0.8780.

110 g of the polymer and 10 g of tetraethylene pentamine were placed in a SOO cc reaction flask, the system was flushed through with nitrogen for 15 minutes and the temperature was increased to 65 ° C. in the process. The temperature was increased to 270 ^° C. within 25 minutes; at 270 ^° C. a vacuum of 15 cm was applied. These μ conditions were maintained for 67 minutes, after which the reaction product was allowed to cool to room temperature under the reduced pressure. The polymer was washed with water and freed from solvent; it had the following properties: KV at 30 ^° C. = 5082 cP; KV at 99 ° C = 198.85 cP; spec. Weight = 0.8852; Iodine number 28.7, nitrogen = 2.00%.

The C = N bond was determined by infrared analysis and the structure was identified as an imidazoline structure determined some existing amide.

The polymer was used as an ashless cleaning agent in a neutral 95 V. I. Mid Continent oil in tested the Sinclair Low Temperature Detergency Bench test described in US Pat. No. 3,044,860; the results are given in Table 3.

Table 3

Base oil

Base oil + 2% additives

valuation
(100 = clean)

22nd
55

The linoleic acid used in Example 1 has the formula

CH ₃ - (CH ₂ J ₄ - CH = CH - CH ₂

, y - CH = CH - (CHJ ₇ - COOH

and therefore the carboxyl group is from the closest ethylenic or olefinic bond separated by a paraffinic chain of 8 carbon atoms. According to Examples 2 and 3 methyl oleate used has the formula

CH ₃ - (CH ₂ J ₇ -CH = CH- (CH ₂ J ₇ - COOCH,

and the carboxyl group is therefore from the olefinic by a paraffinic chain of 8 carbon atoms Bond separated.

Claims (1)

Patent claims: 1. Lubricating oil preparations, consisting of a larger proportion of a base oil with a lubricating viscosity and a minor proportion of an oil-soluble condensation reaction product (A) an oil-soluble polymer containing a) about 3 to 55 mol percent of a compound of general formula RCOOR ', in which R stands for an ethylenically unsaturated hydrocarbon radical with 2 to 25 carbon atoms, R 'represents a hydrogen atom or an alkyl radical mit.l to 15 carbon atoms, and the COOR 'group on an aliphatic carbon-carbon chain is bonded with at least 2 carbon atoms of the group R, b) about 5 to 30 mol percent of a conjugated, diethylenic unsaturated, aliphatic hydrocarbon with 4 to 12 carbon atoms and c) about 92 to 15 mole percent of an α-monalkene having 3 to 25 carbon atoms, the RCOOR 'and the a-monalkene are chosen so that the total number of carbon atoms in these components is at least about 12 and (B) a polyamine of the general formula