DE1594610A1 - Lubricating oil preparations - Google Patents

Description

Many of the "passenger cars currently in traffic" are mainly used to drive to and from work, for shopping and other, short Rides. Such driving takes place with frequent stops and does not result in complete warming up or utilization of the automobile. The engines are only loaded so little and not operated continuously that they are barely warm enough to be effective. The one in such

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The fuel used in engines is of course gasoline, which is known as an easily combustible fuel. Gasoline is easily burned when the engine's combustion chamber reaches a sufficiently high temperature and the fuel in it is appropriately vaporized and mixed with sufficient oxygen. With such a combustion the gasoline is completely burned and only harmless carbon dioxide gas and water vapor are formed. However, if the engine does not work long enough ^{to heat its cooling water and crankcase to at least 65 0} O, some carbon dioxide and water vapor escape through the piston rings, condense the cold crankcase and form liquid carbonic acid, which rusts iron and steel.

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 burned, and a lot of carbon, gaseous carbon monoxide, is formed, partially oxidized gasoline, and highly corrosive fuel acids in the combustion chambers (and additionally to the usual carbon dioxide gas and water), which escape through the piston rings and contaminate the crankcase oil. The material resulting from the incomplete combustion of gasoline causes numerous and often costly engine damage Damage if it collects in the crankcase. Such damage is e.g .: seized and defective hydraulic Valve lifters; worn flakes of the cam disc; fixed piston rings; high piston ring and cylinder wear with correspondingly high oil consumption and oil pollution; corroded bearings; damaged pistons; clogs · oil pump strainers, which leads to an interruption of the engine oil supply can lead; burnt out bearings and seized up ©

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Pistons «A modern lubricating oil must therefore prevent the build-up of solid products on the engine surfaces that would normally come into contact with the lubricant.

Another source of problems from deposits in internal combustion engines are those commonly found in the internal combustion engine Additives incorporated in lubricants. This is especially true for metal-containing additives, such as the organic, metal-containing salts that the oil has to increase its cleaning power be incorporated. Is the oil burned in the engine (as is the case with the oil film present in the cylinder wall during The piston stroke takes place), so all those present in the oil can Metal-containing additives form ash that is partially deposited on the various surfaces of the combustion chamber, spark plugs and valves. Aim of the present Invention is therefore the creation of a lubricating oil preparation,

cleaned with metal- or mineral-free cleaning agents

miaoht is.

Another main supplier of hot water deposits is the incompletely burned gasoline, especially the metal additives contained in the fuel. Ash-free cleaning agents prevent the formation of silt in the engine and disperse any sludge that may have formed. For many years, the main detergent additives used successfully have been organic, metal-containing compounds, such as calcium petroleum sulfonate, calcium cetyl phosphate, calcium octyl sulicylate, caloium phenyl stearate or the potassium acid of the reaction product Phosphorus penta sulfide and polybutene. Various of these Cleaning agents act through chemical reaction with precursors to form harmless compounds.

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prevent the flocculation or coagulation of solid particles in oil and keep it in the state of a suspension of finely divided particles. Other materials not only have this dispersing puncture, but they also affect the solubilization or emulsification of the sparingly soluble monomers in the oil and therefore reduce the rate of polymerization significantly. In the latter case, the polymer materials that form within the oil are smaller and can be peptized or dispersed much more easily in oil than is the case with large polymer particles that are formed on the exposed engine surfaces or in droplets within the oil . The cleaning agents with a dispersing as well as solubilizing or emulsifying function are preferred where possible, especially in motor vehicle engines that are to be driven in city traffic.Although these metal-containing organic compounds are effective as cleaning agents for dispersing these deposition precursors, they have the disadvantage of ash deposits in the engine to build.

In order to circumvent the problems of metal-containing organic cleaning agents, non-metallic cleaning agents have been developed. Sulfurized and phosphosulfurized, long-chain hydrocarbons have cleaning properties; However, these cleaners on heating hydrogen sulphide and form 0.1-0.2 i> ashes. Some detergency has been found with macromolecular compounds, mainly phenols and phenolic resins. Acrylate polymers were also used, and part of the carboxyl function was esterified or amidized with long-chain, oleophilic alcohols and the remainder with hydrophilic polyglycol ethers or neutralized with amines.

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Many non-metallic detergents usually have poor easicity and therefore could be harmful The sulfuric acid formed in situ in the oil has no effect counteract effectively. To increase the basicity of the cleaning agent, polyamine salts and amides were considered possible Detergents have been investigated (see e.g. U.S. Patent 3,018,247, which discloses such detergents, e.g. the w-polyamine-substituted monoalkanylsuccinimides).

The object of the present invention is to provide a lubricating oil preparation, in particular the above Avoids disadvantages of known lubricating oil preparations. In particular it is said to contain cleaning agents (detergents) "which produce ashless products of combustion.

The subject matter of the invention is a lubricating oil preparation consisting of a larger proportion of a base oil Lubricating viscosity and a smaller proportion of an oil-soluble condensation reaction product

(A) an oil-soluble polymer with about 3 to 55 mol-56 of a compound of the formula RGOOR ¹ , in which R is an ethylenically unsaturated hydrocarbon radical having 3 to 25 carbon atoms, R ^{1 is} a hydrogen atom or an alkyl radical having 1 to 15 carbon atoms, and the COOR 'group is attached to an aliphatic carbon-carbon chain having at least 2 carbon atoms of the group R, about 5 to 37.5 moles of a conjugated, diethylenically unsaturated, aliphatic hydrocarbon having 4 to 12 carbon atoms and about 92 to 15 moles -56 of a «£ -Monalkens with 3 to 25 carbon atoms, whereby the RCOOR * and the « Ο -Honeken eo are chosen that the total number

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the carbon atoms in these components are at least about 12, and

(B) a polyamine of the formula

NO'

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

In a preferred embodiment of the invention, the cleaning agents added according to the invention consist of about 10 to 25 mol # of the olefinically unsaturated carboxylic acid or its ester, about 5 to 25 mol # of the conjugated diolefinically unsaturated aliphatic hydrocarbon, about 50 to 85 mol- £ of the «£ -olefin and the proportion mentioned of organic amines.

The unsaturated acids or esters of the new basic to form, öllölichen high-pressure additive with the ⁰ ^ olefins and dienes can be polymerized, are acids or esters of formula R-COOR ¹ in which R is an unsaturated hydrocarbon radical with 3-25 Carbon-> atoms, preferably 8-20 carbon atoms. The group R contains one or more, preferably 1-2, olefinic bonds and can, for example, be acetylenic,

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aromatic groups, etc., provided that the carboxyl group (-COOR ¹ ) is attached to an aliphatic, including cycloaliphatic, carbon-carbon chain having at least 2, preferably at least 8 carbon atoms. R is preferably an unsaturated alkyl radical. R ¹ represents a hydrogen atom or an alkyl group having 1-15 carbon atoms, preferably a lower alkyl group having about 1-3 carbon atoms. If R * stands for 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 : Oleic acid, linoleic acid, undecylenic acid, linolenic acid, ricinoleic acid, methacrylic acid, etc. It is also possible to use the lower alkyl esters of these acids including the glycerides, especially the methyl esters.

The oC olefins or «C monoalkenes can be represented by the formula :

R '- CH - CH =. CH ₂ R "

in which R ¹ and R "each stand for a hydrogen atom or an alkyl group, including a cycloalkyl group, the total number of carbon atoms being between about 32 and preferably about 12-21. One of the groups R ¹ and R" is suitably a hydrogen atom and the other for a straight chain alkyl group to give an n-olefin. The <£ olefins are often used as a mixture and can be used in small amounts, usually less than

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10 wt .- #, of other hydrocarbons, such as other olefins, Diolefins, saturated hydrocarbons and aromatics contain

The conjugated, diethylenically or diolefinically unsaturated, aliphatic hydrocarbons used in the polymer include the polymerizable conjugated, diethylenically unsaturated alkenes with 4-12 carbon atoms, preferably 4-5 carbon atoms, such as κ · Β · conjugated ^ diolefins with a terminal double bond, such as 1, 3-butadiene, isoprene, etc. The diolefin can be substituted by halogen atoms, etc. as long as the substituent {- does not interfere with the polymerization or has any other adverse effect. A substituted, conjugated diolefin is 2 _f B. chloroprene.

The choice of the unsaturated acid, the conjugated, diethylenically unsaturated, aliphatic hydrocarbon and -olefin, their proportions and the hatred of conversion are made in such a way that an oil-soluble polymer is obtained; Usually the total number of carbon tones in the acid and in the "C -Honoolefin" is at least about 12, usually at least about 18 ". For the production of a given polymer, more than one acid, more than" in conjugated, diethylenically unsaturated, lipnathic hydrocarbon or more can be used can be used as an "ε-olefin, and small amounts of other polymerizable monomers may be present"

The polymer can be prepared by reacting the oC-olefin, the diäthylenisoh unsaturated, conjugated, aliphatic hydrocarbon and the unsaturated acid or ester of a polymerization temperature from about O - 50 ⁰ O preferably, about 0 - 25 ⁰ O, "in the presence Ines

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strong Friedel Grafts catalyst such as aluminum chloride or boron fluoride. A preferred catalyst is aluminum chloride. It is convenient to add the unsaturated acid and the conjugated, diethylenically unsaturated, aliphatic hydrocarbon to the & -olefin. A catalyst can also be used which is usually present in an amount of about 0.5-5 volumes per volume of the acid, - - olefin and diene feed. Corresponding cocatalysts are the lower alkyl halides, especially ethyl chloride, methyl chloride, etc.

The strong Friedel-Crafts catalyst is generally present in the catalyst solution in a concentration of about 0.5-15% by weight, preferably about 2-7% by weight; the amount of I'riedel-Crafts catalyst used is usually about 0.1-20% by weight, preferably about 2-15% by weight, of the polymer formed over the proportion of the catalyst that may be present with the carboxyl group of the acid reacts. The ratios of conjugated, diethylenically unsaturated alkene, unsaturated acid and ° C. olefin to the catalyst solution can be between about 1: 2 to 1:10, even about 1: 4 to 1: 5 mol of the reactants per mol of catalyst solution. When the acid form is reacted, at least 0.5 mole of catalyst per mole of acid is usually used in the reaction mixture. The polymer can be formed by the simultaneous addition of the catalyst solution and the mixture of unsaturated acid, conjugated, diethylenically unsaturated alkene and oC -olefin to the reaction vessel. The volumetric ratio of the catalyst solution to the reactants in a given unit of time is often about 2 s 1 to about 4: 1, preferably about 3: 1.

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holders after the addition of catalyst and reaction part · "the polymerization is continued take short time _allowed} ie, generally about 5-45 minutes to complete the polymerization au a öllösliohen polymer, such as a normally liquid material having a kinematisohen viscosity of about 25-1000 oentistoke at 99 ⁰ C, preferably about 30-150 or centistoke to about 300 to ensure. The polymerization can then be terminated by using a lower alkanol, for example having 1-4 carbon atoms, in solution in a lower alkane. The polymer obtained can be separated from the remaining catalyst, for example, by washing with water, alcohol, dilute sodium hydroxide solution, hydrochloric acid or other suitable hydrolysis and washing processes.

The ash-free cleaning agent is produced by condensation of the polymer made from ole fi n , conjugated, diethylenically unsaturated alkene and unsaturated acid with a practically aliphatic polyamine. Suitable polyamines can be represented by the following formula

R ^N M (R »HH) _n H

in which R ^{1 is} a divalent alkylene radical having 2-14 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, which have, for example, 1 to 30 or more carbon atoms, preferably 1 to about 7 carbon atoms; η is a number with a value from 1 to 10, preferably about 2 to 6 «

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R can extend as little as 2 nitrogen atoms, E.B. the two to which R * is bonded, and in this case these nitrogen atoms have only one more, free bond The substituents R and R * can be unsaturated, but are preferably saturated; you can't with interfering substituents, in particular lower alkyl groups, be substituted Amlngruppe primarily 1stι suitable amines can by the the following formula can be represented:

R · R «"

r - i - 6 - iT

R ¹ R ¹ *

where R as above represents a hydrogen atom or an alkyl group, preferably an aminoalkyl group having 1-30, preferably 1 to about 7 carbon atoms R ¹ stands for a hydrogen atom or an alkyl group with 2 - H or more carbon atoms, in particular 2 to about 7 carbon atoms «R can also be a hydroxyalkyl, alkoxyalkyl or aromatic radical ·

The polyamines include monoalkylenediamines, dialkylaminoalkylamines and the polyalkylenepolyamines. Suitable monoalkylenediamines are b.B. Ethylenediamine, propylenediamine, Butylenediamine, ootylenediamine, etc. Suitable dialkylaminoalkylamines are e.g. dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, Methylpropylaminoamylamine, propylbutylaminoethylamine, etc. Suitable polyalkylenepolyamines are b.B. Diethylenetriamine, Triäthylexfetramln, Fetraäthylenpentamin, Hexapropylenheptamin, Xetrabutylenpentamin, Polyamine D (a mixture aliphatic and oyolic poly

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ethyleneamines with a boiling point above 34O ⁰ G and a similar number average molecular weight as penta- · äthylenhexarain that traminoäthylamin as Hauptkoraponenten Pentaäthylenhexarain, symmetrical and unsymmetrical Diamlnoäthyl · * symmetrical Diaminoäthyltriäthylentetramin, symmetrical and unsymmetrical Diaminoäthyl, in Diaminoäthylpiperaz, Pipera zinoäthyltriäthylentetramln, 4- (W -piperazinoäthyl) -triethylenetetramine, Bls-piperaBinoäthylamin and Aminoäthyl- (dipiperazlnoäthan) contains), polyamine H (bottom products from the production of tetraethylene pentamine) etc. Suitable N- (S-aminoalkyl) -piperazines are N-methyl-N'-Cß- aminoäthylJ-piperazine, N- (0-aminoisopropyl) -piperazine etc.

When converting the polymer from an unsaturated Acid or an ester, the conjugated, diäthylenisoh unsaturated alkene and Ulf olefin with an organic polyamine for the preparation of the detergent, the polyamine is usually in a molar ratio of about 0.3-1 Moles per mole of unsaturated acid or ester reacted in the polymer. The molar ratio is preferably between 0.8-1: 1, especially at about 1: 1 · Bas ratio des Polyamines to the polymer can also be expressed in gram atoms of hydrogen-bonded nitrogen in the polyamine per molar equivalent of the earboxyl groups in the polymer. Considering the polyamines of the omel

is therefore a molar ratio of 0.3 to 1, preferably 0.8 to 1, of the polyamine per mole of acid or ester in the polymer is equivalent to 0.3 to 11, preferably 0.8 to 11. gram atoms of the hydrogen-bonded nitrogen

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per molar equivalent of the carboxyl groups in the polymer. The lower limit values are obtained when η = 1 and both R radicals denote hydrocarbon radicals The upper limit value is obtained when η s is 10 and at least one R denotes hydrogen To ensure polymer and to avoid unnecessary crosslinking; if necessary, even a large excess of amine can be present. The reaction usually takes place at a temperature of about 60-32O ⁰ C, which depends on whether an amide or imidazoline formation is desired. They reaction temperature for the amide formation is about 80 ° - 150 ⁰ O and Imidazoline about 250-300 ⁰ C. The reaction is carried out so as to obtain an oil-soluble basic and product. often takes about 0.25-5 hours, preferably about 0.5-3 hours; Water or alcohol is removed as it is formed · That

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polymer obtained is essentially oil soluble and usually has a kinematic viscosity τοη about 1OOO to 20 000 and preferably about 3000- 15000 oentiatoke hei 38 ⁰ Q and a kinetmatische viscosity of at least about 50-1000, preferably about 150-750 ⁰ C. oentiatoke hei 99 the detergent additives are the lubricating oils in small, effective amounts gewöhnlioh between about 0.1 wt -i 10 "or more, preferably about 0.25 -7.5 wt -, ^ was added, based on the oil...

The lubricating oils which can be used as the base oil or main component of the lubricating oil preparations of the present invention include many oils having lubricating viscosities such as naphthenic, paraffinic and mixed mineral base oils; other hydrocarbon lubricants, such as lubricating oils derived from carbon products; and synthetic oils, for example alkylene polymers, such as, for example, polymers of propylene, butylene, etc. and mixtures thereof; Alkylene oxide polymers (ζτΒ. Alkyleneoxy polymers, which are produced by polymerizing the alkylene oxide, e.g. propylene oxide, etc. in the presence of water or alcohols, e.g. ethylene alcohol), carboxylic acid esters (e.g. those produced 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 sutyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, dodeoyl alcohol, etc. ). The above base oils can be used singly or in combination if they are miscible with each other or are made miscible by using common solvents.

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, such as di-2-ethylhexyl sebaoate. Many of these sheet materials are known and their viscosity ranges from light to here

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to heavy oils, β.B. about 50 SUS at 38 ⁰ C to 250 SUS at 99 ⁰ O ₁ preferably 30 to 150 SUS at 99 ⁰ O. These Seter have an improved heat resistance, a lower acid number and high flash and fire points. The complex esters, diesters, monoesters and Polyesters can be used alone; To achieve the most suitable viscosity properties, complex esters, diesters and polyesters can be mixed with one another or with naturally occurring esters such as castor oil to obtain Sohmler products, the wide viscosity ranges of which can be precisely matched to the various purposes Amount of diester and complex ester stirred together at elevated temperature; the proportion of each component being changed until the desired viscosity is achieved. The mono- and dicarboxylic acids used to make the synthetic ester base stocks can be branched or straight chain and saturated or unsaturated and often contain about 2-12 carbon atoms. The alcohols usually contain about 4-12 carbon atoms. Suitable glycols are generally the aliphatic monoglycols having 4-20 or 30 carbon atoms, preferably 4-12 carbon atoms.

Materials can be added to the preparation according to the invention that are usually used in lubricating oils to give them special properties. These include corrosion inhibitors, anti-wear agents, anti-wear agents, etc. Those used in the preparation The amount of such additives is usually between about 0.01-20% by weight or more; in general, Bie in any desired amount can be used as long as the preparation is not adversely affected.

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The following examples illustrate the present invention without limiting it.

example 1

To a mixture of Oi -olefins with approximately the following composition:

Qew.-jC

total olefins 95+

total <A olefins 94

straight chain g { olefins 86

branched and naphthenic olefins 3

straight chain d, ^ diolefins 6

saturated and aromatic hydrocarbons 4

Molecular weight distribution, Number of carbon atoms

14 1

15 12

16 '19

17 18

18 18

19 17

20 14

21 1

isoprene and linoleic acid were added in a molar ratio of O ^ -olefin to isoprene to linoleic acid of 6.65 / 2.45 / 1.0, based on the average molecular weight (243) of the U -olefin mixture. A 1 liter flask was fitted with a Dean-Stark trap and two addition funnels. A dry ice trap was placed on top of the Dean-Stark trap to remove and condense the volatile solvent ethyl chloride used in the polymerization.

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aäure / diäthylenißch unsaturated alkene fed into the other funnel a Xatalysatorlösung of 5.2 g of aluminum chloride per 100 cc of ethyl chloride was added at 12 ⁰ C.

The feed of the Reaktionateilnehmer and the catalyst solution were simultaneously introduced into the reaction flask and that the mixture of olefin and Lelnölsäure diäthylenisch unsaturated alkene at a rate of 24.2 cc per minute (0.0615 moles per minute CJJ _C-21 A. - Olefin, 0.026 mol per minute isoprene and 0.00923 mol per minute linoleic acid) and the catalyst solution at a rate of 49 cc / min (0.0192 mol / min. J -aluminum chloride). The total addition time was 10 minutes, then the polymerization mixture was stirred for an additional 20 minutes. The temperature during, polymerization was 16 ⁰ C, and there were 320 cc (61? S) Xthylohlorid removed by Ealie from the polymerization system. To quench the catalyst, 400 ecm hexane and 400 com isopropanol were added.

The polymerization was washed with dilute hydrochloric acid and a further 3 times with water. It was freed from solvents and had a KV of 3603 it at 38 ⁰ C; K? of 199.54 it at 99 ⁰ C; Acid number * 25.44; Iodine number -,

43.9 »spec. Weight *> 0.8778.

100 g of the above polymer and 8.0 g of tetraethylene pentamine were placed in a 500 cem reaction flask; The system was flushed with nitrogen within 15 minutes, the temperature was raised to 65 ⁰ C. The temperature was increased to 270 ^° C. within 20 minutes; a vacuum of 15 cm was applied ^{at 270 °} C. for 75 minutes to facilitate the removal of water. Under this reduced pressure the temperature would drop to room temperature

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calmly. The product was washed and the solvents removed. The polymer had a spec. Weight *. 0.8933} KV 13 500 it at 38 ⁰ Cj KV 550.63 it at 99 ⁰ Cj iodine number «47.4; and 2.51 nitrogen x Infrared analysis revealed the CsN bond and confirmed the imidazoline ring structure with a trace of amide present. Pas polymer was as ash Losee detergent in a neutral Vl 95 Mid Continent oil in the process described in U.S. Patent 3,044,860 Detergenoy Benoh test at. low temperature · The results were tested wi · follows: ι

Rating (100 = clean)

Base oil 22

Base oil + $ 2 additive 87

Example 2

The same reaction apparatus as in Example 1 was used. To a mixture of the olefin feed ck according to Example 1 were placed in a molar ratio of methyl oleate to butadiene to 4 olefin of 1, 1,3-butadiene and Methylolsat: 3: 4, based on the average molecular weight of d -Olefinmisohung added. In a BeschickungsgefäS the olefin / methyl oleate / butadiene was feed and introduced a Katalysatorlöeung of 5.2 g of aluminum chloride per 100 cc at 12 ⁰ O Äthylohlorid in the other vessel. The olefin / acid mixture and catalyst solution were simultaneously introduced into the reaction flask, with the olefin / acid mixture at a rate of 19.6 cm / 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 (5715 J *) were removed from the system using a trap. The catalyst was using

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400 com hexane and 400 ecm isopropanol quenched. The polymer was washed with water and freed from solvents. It had a saponification number of 38.0; spec, weight ■ 0.8897? Iodine number 32.0; KV. 1317.0 it at 38 ⁰ C; KV

To 200 g of the polymer were ^{added 26 g (Eetraäthylenpentarain at 26 0} C. The system was flushed with nitrogen and the temperature ^{increased to 270 0} C within 50 minutes; a vacuum of 19 cm was applied for a further 90 minutes. The reaction product was under This reduced pressure was allowed to cool to room temperature and had a nitrogen analysis of 3.69 #.

The additive was tested in the CLN oil test engine at 1- $ 6 concentration using the "Motor Car Manufacturer's Sequence SA for Motor OiIa for Service MS ^M method ". The details of the Bind method are given in Table 2 below.

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σ ο

Table 2

Test duration: 24-0 hours; no oil filter; no oil change; oil feed: 0.95 1; oil added as needed; Fuel: "certified MS 08"; after 61 3/4, 125 3/4 and 189 3/4 hours, samples of 56 g were removed

Phase time rev / min approximate ignition APR approximate operating temp.

Torque forward feed: stainless std mixture

1 45 min 550-650 Idle (0.2) 14 38-52 9.5-10, 5 Feeding air ⁰ C co
co 2 2 hours 1790-1810 W.O.T. (3.5-5) 14 71-77 15.5-16, 5 0.6-0.7 6-7 90.5-96 v » "Blow by
CHP " Outlet oil ^w Gallery "
temp. of water ⁰ C
⁰ C approximate
oil pressure 4.5 70 35-40.5 ° cn
cn ._ 50.5-55 20th Temperature difference
between water entry
and exit; ⁰ C record 50.5-55 40 0.5-1.1 2.2-2.8

I. cn CO VO -E- I. CD O

The cycle was repeated 5 times (13 3/4 hours in total). The motor was turned off and water at 95-97 ⁰ C for 2 1/4 hours circulated (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 breathing time of 240 hours.

The results are given in Table 3.

Table 3

• Basic mixture I. Basic mix + 1 %
Additives Time to the start of
Deposits; hours 96 224 final evaluation after
240 hrs T50-100 $ clean) 24.9 45.8 Example 3

The same reaction apparatus as in Example 1 was used. To a mixture of the o ( -olefin feed according to Example 1, isoprene and methyl oleate were added to a molar ratio of # -olefin / isoprene: methyl cleate of 6.05: 2.05 ^ 1.00 based on the average molecular weight of the of-olefin mixture The polymerizer was the same as in Example 1. One funnel was charged with the reactants, the other with a catalyst solution of 5.2 g of aluminum chloride per 100 cc of ethyl chloride the olefin mixture at a rate of 20.8 ccm / min (0.0525 mol / min c ( -olefin, 0.0173 mol / min isoprene, 0.00860 mol / min methyl oleate) and the catalyst solution at a rate of 39, 5 cc / min (0.0154

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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 0} O, and 280 ecm (59 SO x ethyl chloride were removed from the polymerisation system by means of a trap. 400 ecm hexane and 400 ecm isopropanol were added to quench the catalyst. The polymer was washed with water and, after removal of the solvents, had the following properties; KV at 38 ⁰ C «1190 es; KV T> ei 99 ⁰ O« 94.54 ce; iodine number = 30.7; saponification number = 24 »3; food weight ■ 0.8780.

P In an SOO-cc reaction flask was added 110 g of the polymer and 10 g of tetraethylenepentamine added, the system flushed 15 minutes with nitrogen and the! Temperature thereby increasing to 65 ⁰ C. Within 25 Hinuten the temperature was raised to 27O ⁰ C; at 27O ⁰ C, a vacuum of 15 cm was used "These conditions were maintained for 67 Hinuten, was allowed to cool and the reaction product under the reduced pressure to room temperature. The polymer was washed with water and freed from solvent; it had the following characteristics:

at 30 ^° C. 5082 ob; KV at 99 ⁰ C "198, 0.8852; Iodine number 28.7? Nitrogen ■ 2.00

KV at 3O ⁰ C ■ 5082 it; KV at 99 ° C »198.85 ce; spec. weight

The C = sN binding was determined by infrared analysis and the structure determined as an imidazoline structure with some amide present.

The polymer was tested as ashless detergent in a neutral Vl 95 Mid Continent oil in the process described in US, Patent 3,044,860 Sinclair Low Temperature Detergenoy Bench Test; the results are given in Table 4.

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Table 4

Rating (100 = clean)

Base oil 22

Base oil + 2 Ί * additives 55

The linoleic acid used in Example 1 has the formula CH ₃ - (CH ₂ J ₄ -OH = CH-CH ₂ -CH = CH- (CH ₂ J ₇ -OOOH, and therefore the carboxyl group is from the closest ethylenic or olefinic Bond separated by a paraffinic chain of 8 carbon atoms. The methyl oleate used according to Examples 2 and 3 has the formula CH, - (CH ₂ ) »- CH = CH- (CH ₂ )« - COOCH «, and the carboxyl group is therefore through a paraffinic chain of θ carbon atoms separated from the olefinic bond In each case the paraffinic chain is CH- (CH ₂ ) ,,.

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BATH ORIGINAL

Claims (1)

Pa t e π t a η ο ρ r ϋ ο h e 1e Fcrm * pyolrT'cvPZ "'*' " h ~ nt? H ^ nd .111 * 1 etr-p · ⁵ ! * ~? 'ύ Both ^1st . Eineß proportion Grunßö'-s-t rlt Schmienrlokocitä and a lesser proportion of a öa * ¹ "'oil lohen KoiideneaticnH-Reakttonsproduktf; flr ^ r. οι ""i-; ii.Vj-n PcCym ^ x * <rt; * 1 "· 5" tvva 3 "bit 55 Kol-9 eirer Vft.-bxirtii" - _: > der? or> v ^ l RCO'.Tt *, Ir der R for ■■■■ uum * ä ';"'iaifcüh vrTi ^ eeMüU .c jcn iohlen ^ aaseretoffreet rait I hlz 25 f.uhle ^ iitoi'if.tcraan, B ¹ for a ViiiiiafeJ! ö \ c., -'.,. rt'vc-iu οάύϊ" · fiiii;.: - i; U kjiV .x ^: eß'Ji aiii; 1 to 15 for. Lenst *?. IruT »-: K s ^ oh *, ^ r;. · * ·. i: .. ^ OOOIl '-Gr ^ ppe an ^ fil; l- _t ' rti ^ -ie Koalerciioi ^ r-carbon chain with at least <? K> ileti8toif atoms (he group R bound iöt, about 5 b -. ^ 30>'ol-5f eiuee i.cn ^ ug-i i; rten, diethylonlsch uij ^ eteil:
stcffs w'i> ^Λ >''.
"bie15'Mcl- *» e- * nee 0 { -Monalkenjp alt 3 "to 25 carbon atoms ,, μ at ύ & ζ KCDOK» v; id the ^ -ftonalken ve, -ai, ΐ £ · £ ·!.: . _t > ^^ ös.staaiil der lohlen «* b; i # ißcn Tiompo.i ^ atä: a aLlt '^ eeter / .a about 12, and (B) a ioljau ^ rr dar? Orael R _v ft " in which R ¹ stands for a divalent alkylene radical with 2 "to 14 carbon atoms, R stands for a hydrogen atom or a hydrocarbon radical with 1 to 30 carbon atoms, and η represents a number with the value from 1 to about 10, in an amount of approximately 0.3 "to 1 Koi per mole RCOOR · in the component (A). 009824/1575 BAD original ' - ^ -irat according to claim 1 » characterized by _f niiii tr airier amount of O ₁ '-! Ma 1 mole each -;,;. der TIuöp; -ßeite (A) oiiywös -: -. ; .d Lst- _? and B ^f -: .-, '! for 2: La 7 K ο hl? ntri ;;, i ■; jtooie _f R for . ■;> - ^A .-...; ->. ': Alk / Irei /: ei, /. 1 jL:, 7 coals « * ■ Lr, - ¹ .: ", Train."'.-- ii ^ r- + ^ "f 1st, and R ^f .-! pi ■ ... · .; :. · L ..β. - ^ I ^ ruii genor · '- ■ ■',> .ϊ: T · ■ -; r ■ i taylen— ■? *:.: ■. · ■ "!: ■. ·? Ϊ́ν ·; 1, related (A. ov ^r - ^ii;> '■■ ''■' ■ "■ ^: ' ^: ' ■ '■■. ■''Sken- n. draws ν.- rti ./u.>;; d .-. r / onnel RCOOR, : ... '.:> ■■: "■ ;. ι ^: -" - ^{: i} :]. ^; rU:, - t; n Alkylreat '.orae ,: iXf'M.;.,., _A id R ¹ a water -., er ι. · ". - til : .i., 5 Mb 25 ■ vh ge ·: ') Ge ™ : i; e, yii ■ - Bi Li ..; l BATH ORIGINAL