DE1645056A1 - Lubricants and fuels - Google Patents

Description

DRS. OWL & MOUNTAIN PATENT LAWYERS Dw. F ul> & Barg, DIpI. lug. Stapf, «MOndnn 13. KurfOrcf nplotz

Attorney's file: 14

• MÜNCHEN 19, the 2 7.

KUlK) RSTINNATZ 2

Tt ^ romm-Adr .. FATENTfUIi MI »*« loKkvtrblndiinai • oywiMk · VanlMlMnk Mlndwi 4SS100

"S3"

UnHrZMdMn

Lubricants and fuels.

The present invention relates to certain new ships ache bases and bis-Schiff bases which can be used as detergents in sci-oil preparations.

$ 66

i'ntor the conditions to a great extent at present

000820/1672

-2-

1645058

Kraftfal.rzeugverkehr (for example the so-called "stop and go driving") are given, reach respectively. automotive engines do not maintain their most desirable and efficient operating temperatures. As a result, v / ground large oil insoluble know Oxydationsi roducts formed which come optionally in the crankcase by flow past the piston rings. Since most of these products are oil insoluble, they tend to build up on the internal parts of the .iasehine, making the machine more inefficient.

In today's practice, the deposition of oxidation products is reduced by adding detergents to lubricating oils incorporated, which keep the oxidation products in dispersion. In general, .lie are common today Compounds containing detergents I-detail. However the use of ketal containing detergents has not been entirely satisfactory as such detergents Ash deposits in the combustion chambers Engines form, which contaminates the spark plugs and other problems such as pre-ignition occur.

It has now been found that by using of metal-containing additives caused problems through the use of certain new non-metallic ones Connections can be eliminated, welct.o effective

009820/1672

-3-

-3-ashless detergents or dispersants and Schiff

see bases of the general formula

RC = N- R ₁ -

1 \

R ₅ R ₃

and bis-Schiff »see bases of the general formula

RC = HR ₁ -N = C-I

are, where R is a polymer of a lower olefin, the polymer having a molecular weight of about 5Cv to about 30Ü0, R ₁ alkylene, phenylene, alkylphenylene, haloalkylene, halohenylene, a hydrocarbon chain with from 4 to 16 carbon atoms and from 1 to 6 nitrogen atoms, the hydrocarbon chain optionally containing from about 1 to 4 piperazino, phenylene and / or aminophenylene radicals, and / or a substituted hydrocarbon chain, the substituted hydrocarbon chain containing from 4 to 16 carbon atoms and from 1 to 6 nitrogen atoms and the substituent Alkyl, amino-alkyl, alkyl-amino-alkyl, dialkylanino-alkyl, N-ri ^ erazino-allryl, alkyl-oiperazino-alkyl and / or a hydrocarbon chain with from 4 to 8 carbon atoms and from 1 to 3 nitrogen atoms, the said

-4- 009820/167?

-4-

Hydrocarbon chain optionally contains from about 2 to 4 piperazino radicals, R ₂ and R, identical or different and can be hydrogen, alkyl, aryl, aralkyl, alkaryl, haloalkyl and / or haloaryl, R. R, hydrogen, alkyl, aryl , Aralkyl, alkaryl, haloalkyl and / or haloaryl, R ₁ - hydrogen and / or alkyl, R _fi R ^, water

^{0 p} and /

substance, alkyl, aryl, aralkyl, alkaryl, haloalkyl or haloaryl can be.

The new ship see bases of the present invention can be made by implementation

(a) a long-chain ketone or aldehyde of the general formula

Il

TJ f * t TJ

and

(b) a diamine of the general formula

wherein R, R ₁ , R ₂ , R, and R ^ have the meaning described above. Usually the col ratio of (a): (b) is approximately 1: 1. The reaction can be carried out by simultaneous. Mixing (a) with (b) or by adding one of the

003820/1672

-5-

tion3partners to the other, whereby the order of addition of reactants is not critical. A hydrocarbon solvent such as a short chain aliphatic solvent or aromatic solvents such as toluene or xylene can be used. A mineral oil or distillate oil can be used as a diluent, either alone or in conjunction with a hydrocarbon solvent. The Rea- *

tion temperature can be from about 50 ⁰ G to 250 ⁰ C, preferably from about 80 ⁰ G to 150 G with a reaction time of about 2 hours to about 8 hours. This reaction can be carried out under atmospheric pressure or reduced pressure can be used to facilitate the removal of reaction by-products such as water.

The bis-Schiff bases of the present invention can are produced by implementation '

(a) a long-chain ketone or aldehyde of the general formula

• ι "

RCR ₅

(b) a diamine of the general formula

NH ₂ - R ₁ - NH ₂

and 000850/1172

-6-

(c) a ketone or aldehyde of the general formula

R ₄ - C - R ₆

wherein R _1, R ₁ , R., R ₅ and Rg have the meanings described above / Normally the molar ratio of (a): (b) :( c) will be approximately 1: 1j1, but the reactant (a) can be in excess up to about 20? ' can be used to ensure a complete reaction, with no adverse effects occurring as a result of the detergent effect due to the unreacted reactant (a) remaining therein. The bis-Schiff ¹ see bases can be prepared by mixing (a) :( b) :( c) together or in any order of addition of reactants to produce the bis-Schiff bases of the present invention. A Koh - Ienwas3ero ⁱ tofflösungsmittel such as toluene or xylene, or a mineral oil alone or in conjunction with another hydrocarbon may be used to facilitate the removal of water. The reaction temperature may range from about 50 ⁰ C to 250 ° C, preferably from about 80 ⁰ C to 150 ⁰ C with reaction times amount of about * 2 hours to about 8 hours. The reaction can be carried out at atmospheric pressure or reduced pressure can be used to facilitate removal of water when no solvent or a mineral oil solvent is used.

82Q / U72

The reaction is usually carried out under an inert atmosphere such as nitrogen, but reaction conditions can be used to prepare the compounds of this invention "for example an air atmosphere being used and reaction temperatures below 100 ° C."

It is also contemplated in the present Erfindimg that _f if the bis-Scliiff ·· see bases upstream of the

lying invention additionally contain unreacted primary and secondary amino groups, ie R ₁ contains primary or secondary amino groups or both »that these bis-compounds can then be further reacted with · (a) or (o) or mixtures thereof, in which (a) and (c) are as defined above for the preparation of compounds and a mixture of compounds which in turn are useful as lubricating oil additives. Although the exact structure of the new compounds and mixtures of compounds cannot be readily ascertained, they can be described by their method of preparation. The process is carried out by mixing (a), (b) and (c) in any order or simultaneously, the molar ratio of the sum of (a) and (c) to (b) from about 2.1: 1 to about 4t1, preferably from about 2.1: 1 to about 3: 1, provided that there is at least 1 mole (a) and 1 mole (c) and the mixture is heated for about 1 hour.

009820/1672

-8th-

de takes place to about 36 hours, preferably from about 2 to about 16 hours at a temperature of about 5O ⁰ C to about 30O ⁰ G, preferably from about 70 0 to about 200 ⁰ C. A hydrocarbon solvent such as short chain aliphatic and aromatic solvents such as toluene and xylene can be used as a diluent to facilitate removal of reaction by-products such as water. A mineral oil or distillate oil can also be used as a diluent, either alone or together with a hydrocarbon solvent. This reaction can be carried out at atmospheric pressure or a reduced pressure can be used.

The intermediate long chain ketone

Il

R - C - R _K
0

wherein R and R, - can have the meaning described above are produced by reacting an olefin polymer or olefin copolymer or mixtures thereof hereinafter referred to as polyolefin - having a molecular weight from about 500 to 300C, preferably from about 700 to 2000, with O'ion to form an ozonated Polymer. Preference is given to a polymer of a lower olefin or a copolymer of lower olefins

used, for example, polymers of ethylene, prorulene, Ö0982Q / 1672

Butylene, isobutylene or mixtures thereof. Copolymers which can also be used are copolymers of lower olefins and diolefins, such as 1,3-butadiene and isoprene. Before the olefin polymer is brought into contact with ozone, a short-chain alcohol having from about 1 to 12 carbon atoms, preferably from about 1 to 8 carbon atoms, is added to the polymer. The alcohol is typically in a molar ratio to the olefin polymer of from about 1 to 40 moles of alcohol per mole of λ polymer, preferably from about to 10 moles of alcohol per Koi polymer before. A diluent such as a lower hydrocarbon solvent or a mineral oil or distillate oil can also be used, either alone or in conjunction with a short chain hydrocarbon solvent. The polymer-alcohol system is brought into contact with ozone in an amount of 0.50 l-iillimols per minute of ozone per mole of polymer to about 10 millimoles per minute of ozone per mole of polymer, preferably of about 1 millimole per minute of ozone per mole of polymer to about 6 millimoles per minute of ozone per hol polymer. The reaction can proceed at a temperature of -50 ⁰ C to +50 ⁰ C, preferably from -30 ⁰ C to 3O ⁰ C are performed. The reaction is generally carried out over a period of time which is sufficient for the ozone supply to be approximately equal to the amount of ozone exiting.

Typical examples of amines used in the manufacture of 009820/1 67 ^

-10-

Compounds according to the invention that can be used are diethylenetriamine, di (methylethylene) triamine, triethylene tetramine, tri (methylethylene) tetramine, tri (ethylethylene) tetramine, tetraethylene pentamine, pentaethylene hexamine, ethylene diamine, hexamethylene diamine, o-phenylene diamine, p-phenylene diamine, m-alkylene diamine -substituted o-, m- and p-phenylenediamine, dimethylaminomethylamine, dimethylaminoethylamine, dimethylaminopropylamine _? Dimethylaininobutylamine, Dimethylamineheρtylamine, Diethylaminomethylamine, Diethylaminopropylamine, Diethylaminoamylamine, Dipropylaminopropylamine, Ethylpropylaminoaiaylamine, Propylbutylaminoäthylamin, Dimethylene trianiline, Lethylene dianiline, Polymethylene aniline, like an anilene dianiline, are treated in the presence of an anilene dianiline, the presence of an anilene dianiline, polymethylene aniline in the presence of an acid, an alylenesaniline, the presence of an anilene aniline, the presence of an anilene aniline, the presence of an anilemethylene aniline, and the presence of an anilemethylene aniline. When formaldehyde is reacted with aniline, it forms polymethylene aniline.

Typical examples of polyamine mixtures are those under the names Polyamine K, Polyamine H and Polyamine D from the Union Carbide Chemical Go. distributed products. These polyamines are most easily made by the reaction of ethylene dichloride made with ammonia. "This process leads to the production of somewhat complex mixtures of ethylene amines, including cyclic condensation products such as piperaines and these mixtures are found in the invention Procedure use. On the other hand you can

009820/1672

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quite satisfactory products can also be obtained with the use of 'pure ethylene amines, as described hereinbefore'. A particularly useful ethylene amine, both for reasons of economy and because of its effectiveness as a dispersant, is a mixture of polyethylene amines produced by the reaction of ethylene chloride and ammonia, which has a composition that corresponds to that of tetraethylene pentamine. These fi-emieche are commercially available under the names ^M Po- | Lyamin H ⁿ and "polyamine ii available polyamine M has the following properties:.? 34, ¹ ^ nitrogen, 14.7 $ primary amine, Durchscunittsiaolekulargewicht of 212 and a distillation distribution of 10 5 at 137 ⁰ O, $ 50 at 200 ⁰ G . and ÖO? S at 217 ⁰ G at 5 vm mercury. Polyamine D has an average molecular weight of 233 and 31.5 $ nitrogen. Kan assumes that the main components of polyaain D have the following composition:

HH ₂ -OH ₂ -CH ₂ -KH-CH ₂ -OH ₂ -KH-OH ₂ -OH ₂ -IIH-CH ₂ -OH ₂ -IIH-Oh ₂ -CH ₂ -HH ₂ 3,6,9,1 - Tetraaza-1,14-tetradecanediamine

GH ₉ 1 * -

CH ₅

KH ₂

6- (2-aminoethyl) -3,6,9-triaza-i, 11-undecanediamine

009820/1672

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NH ₂ -CH ₂ -GH ₂ -N-CH ₂ -CH ₂ -NH-CH ₂ -OH ₂ -NH-OH ₂ -Ch ₂ -NH ^ CH ₂ CH ₂

NH ₂

3- (2-Aminoethyl) -3, 6,9-triaza-1,11-undecanediamine NH ₂ -CH ₂ -CH ₂ * CH ₂ -OH ₂ -NH ₂

N-CH ₀ -CH ₀ -N

/ ²² X

NH ₂ -CH ₂ -CH ₂ . CH ₂ -CH ₂ -NH ₂

3,6-bia (2-Aiäinoäthyl) -316-diaza-1,8-octandie.min

CH ₅ -CH ₉

N-CH ₂ -OH ₂ -NH-CH ₂ -CH ₂ - ■ ^ΝΗ

_f 4-bis (3-aza-5-aminopentyl) piperazine CH ₀ -CH ₀

_m ^Χ Ν CHp-CHp-lTH-CHp-CHp-NH-

CH ^

KH

1- (2-Aminoethyl) -4- (8-amino-3,5-diazaoctyl) piperazi η CH ₂ -CH ₂

T TUT * ^^

CH ₀ -CH ₂

N- (GH ₀ -GH ₀ -NH), - (

CH ₂ -CH ₂ ^

₂ -OH ₂

1- (11th-Amino-3,6,9-triazaundecyl) piperazine NH ₀ -CH ₀ -CH _n -N-GH ₀ -GH ₀ -NH-CH ₀ -GH ₀ -IiH ₀

GH ₂ OE ₂ Q09820 / 1672

-13-

GH ₂ ^N OH

OH ₉ OH ₉

■ ■ \ /

^N NH
- / 8-AmInO-J- (2-aminoethyl) -3,6-diazaoctyl__7piP ^ei> azine

OH ₂ -OH OH ₂ -CH ₂

HN ' N-OH ₂ -OH ₂ -NH-CH ₂ -OH ₂ -N ^ NH

OH ₂ -OH ₂ CH ₂ -CH ₂ i

11 '- (3-azapentamethylene) dipiperazine CH ₉ -CH ₉

^{2 2}

NH ₂ -CH ₂ -OH ₂ -N N-OH ₂ -CH ₂ -N '

^ / ITT ntr nil nu ¹ ^

'CH ₉ -OH ₉ OH ₉ -CH ₉

4- (2-aminoethyl) -1,1 · ethylenedipiperazine

These ingredients are sold as a mixture, however, it is contemplated by the present invention that the individual compounds themselves can be used as amine reactants. Polyalkyleneimines are also suitable amines and can be prepared by the polymerization of compounds such as ethyleneimine, 1,2-propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 2-methyl-1,2-propyleneimine, trimethyleneimine and hexamethyleneimine using known polymerization processes getting produced. In the Ij.S. A typical polymerization process is described in U.S. Patent 3 20,0 088.
ÜQ9820 / 1672

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As can be seen from the description of the compounds of this invention, the carbonyl containing compound can be an aldehyde or a ketone. The aldehydes useful in making the bis-Sohiff bases of this invention can be aromatic or heterocyclic in nature. Representative examples of such aldehydes where Rg is phenyl and R is hydrogen are benzaldehyde, alkyl substituted benzaldehyde, for example 2-, 3- and 4- ^ methylbenzaldehyde, 2,6- and 3 »5 dimethylbenzaldehyde 2-, 3- and 4-ethylbenzaldehyde, 4-isopropylbenzaldehyde, 2-isobutylbenzaldehyde, 4-ethylbenzaldehyde, 2,3 »6- and 2,4,5-trimethylbenzaldehyde, 2,315,6-tetraraethylbenzaldehyde, 2-hydroxy-5 methylbenzaldehyde, halogen-substituted benzaldehyde, for Example 2-i'luorobenzaldehyde, 2-, 3- and 4-chlorobenzaldehyde, 2-, 3- and 4-bromobenzaldehyde, 2-iodobenzaldehyde, 3> 4-dichlorobenzaldehyde, 2,3,5-trichlorobenzaldehyde, pentachlorobenzaldehyde, 2-trifluoromethylbenzaldehyde, alkoxy substituted benzaldehyde, for example 2- and "3-methoxybenzaldehyde, 4-methoxybenzaldehyde (anisaldehyde), 2-, 3- and 4-ethoxybenzaldehyde, 2,3- and 3,4-dimethoxybenzaldehyde, 4-hydroxy-3-niethoxybenzaldehyde (vanillin) , 3-ethoxy-4-hydroxybenzaldehyde, 3> 4 »5-trimethoxybenzaldehyde, 4 methoxy-3 hydroxybenzaldehyde (Tsova nillin), hydroxy sub / - ^ substituted benzaldehyde, for example 2 hydroxybenzaldehyde _m (salicylaldehyde), 4-hydroxybenzaldehyde, 2-hydroxy-4-chloro-ο benzaldehyde, 2-ethyl-4-hydroxybenzaldehyde, 2,6- and 3, 5-di- - ¹ * hydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde. Other ^ substituents can include nitro as in 2-nitrobenzaldehyde, amino as in 2-aminobenzaldehyde, and 4-diethyl

aminobenzaldehyde, benzyloxy as in 3-benzyloxybenzaldehyde * Carboxyl as in benzaldehyde-3-carboxylic acid, phenoxy as in 2-phenoxybenzaldehyde, vinyl as in 2-vinylbenzaldehyde, j and oyano as in 2-cyanobenzaldehyde.

In the event that Rg is a naphthyl radical and R, hydrogen typical starting aldehydes are, for example, 1- and 2-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 1-hydroxy-2-naphthaldehyde 4-phenyl «2 naphthaldehyde and the like. ■

Where R is furyl and R _{6 is} water, the starting aldehydes include 2- and 3-furfuraldehyde, 4-methylfurfuraldehyde, 5-hydroxy-2 furfuraldehyde, and the like.

If R. is not hydrogen, it is the one containing carbonyl aromatic or heterocyclic compound a ketone, which is aromatic, heterocyclic or mixed Structure to be kartn.

The ketones useful in making the Schiff ¹ bases of this invention are illustrated by the following non-limiting examples: acetophenone, propionphenone, butyrophenone, pelargonphenone, capriphenone, hendecanophenone, acetone naphthone, capronaphthone, arachidophenone, stearonaphthone, benxoin, methyl-2-methyl-2-thyl -ketone, benzophenone, 4,4 ^l -bis (dimethylamino) -benzophenone, 4-kethylbenzophenone, 4,4 ^f -dimethylbenzophenone, 2-, 3- and 4-hydroxybenzophenone, 4 »4 ^f -dihydroxybenzophenone, 1-nai- ethyl

009820/1672 _ ₁₆

-16- '., .- ■ "■' ketone, 4-methyl-1-naphthy 1-1-naphthyl-ketone, 4-methoxy-1-

najAthyl-1 -naphth, / l ~ ketone, '4-Amino-1 -nai ^ hthyl-1 »-naphthylketon, 1-liaplithyl-iJhenyl-ketone furfuryl-ketone,. Methyl furfuryl ketone, Phenyl-furfuryl-ketone, 1-Naplrfchyl-furfurylketone.

The ozonated polyolefin can be "decomposed" in any of the usual ways to form a polyalkyl ketone, such as "with hydrogen over a rare metal catalyst, or" with zinc in acetic acid. After ozonolysis, acetic acid is added to the ozonated polyolefin, followed by adding "and after the mixture zinc dust too. The mixture is then heated to a temperature of 40 = about 0 to about 100 G ⁰ over a period of time sufficient for decomposition of the ozonated olefin. The polyalkyl ketone is obtained by any conventional technique such as solvent extraction and then distilling off the solvent from the polyalkyl ketone.

The following non-limiting examples allow one better understanding of the preparation of the compounds of the invention.

example 1

In a 1 liter 4-neck round bottom flask fitted with a Sehliff 0096 ^ 0/1672 ₁₇

stirrer and a shovel, thermometer, gas inlet tube (for supply below the surface) and exhaust gas outlet pipe is equipped, 200 g (0.2 mol) of polybutene, MoIekul ar weight 985, 9, .6 g of anhydrous methyl alcohol (0.3 Mol) and 300 cc of olefin-free hexane introduced. The mixture was kept agitated by stirring and after a homogeneous solution was achieved, the temperature was adjusted to -75 ° C. by means of a dry ice / acetone bath. Ozone at a rate of 0.855 millimoles per Minute (pre-set using hexane alone) - was introduced. It was complete in 4 hours absorbed; after this period, ozone could be observed in the exhaust gas. The reaction vessel discolored ■ turns blue, indicating the presence of a saturated ozone solution. So much ozone continued to be introduced until the amount introduced was equal to the amount in the exhaust gas stream. The total reaction time required was 6.5 hours. The resulting ozonized ' Polybutene In hexane conmuaen at room temperature, whereby during this, dissolved ozone was flushed out with a stream of nitrogen. ·

B e i s ρ i el 2

CO ■ "_ '■ -." . "" ■■ ■ ■: - -

In a 1 liter 4-neck round bottom flask fitted with a ship

° stirrer and a shovel, thermometer (-50 ° to + 10O ⁰ G),

φ gas inlet pipe (for sub-surface feed) and

»° Exhaust pipe is equipped with 200 g. Polybutene,

■ Molecular weight 1350 (0.15 mol), 250 oe olefin-free

Hexane and 9.6 g (0 _f 5 moles) of anhydrous methyl alcohol were introduced. The temperature was maintained at 25 ° C and ozone was introduced at a predetermined rate of 0.8 millimoles per minute. The ozone was completely absorbed for most of the reaction time and more slowly towards the end of the reaction. When the ozone concentration in the exhaust gas stream was equal to the introduced amount of ozone, the reaction was stopped (8 hours) and the dissolved excess ozone was removed from the unit with nitrogen.

Example 3

The Haxan produced as in Example 1 ozonated. Pplybuten ^ emiach was stripped of hexane under reduced pressure, leaving enough hexane back to slightly remove to keep the solution to be stirred. Into a 4-neck reaction flask equipped with a stirrer was added 200 g of the above polymer and 200 cc of acetic acid introduced. The temperature was 25 ° C and 33 g (0.5 mol) of zinc dust were added in small portions over a period of 30 minutes. The temperature was increased to 35 ° C (maintained by an ice bath) and then the reaction mixture was heated to 65 ° G and at that temperature held for an hour to ensure complete reaction. The reaction mixture was then while it is still hot, filtered by suction for removal "

009820/1672 i

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of zinc acetate and unreacted zinc, and the filter was washed with hexane. The product, in hexane solution, was separated from acetic acid using a separatory funnel. The hexane fraction was washed with water to remove acetic acid. The hexane fraction was dried over sodium sulfate, then filtered, and the hexane was removed under reduced pressure to give polybutyl ketone as a viscous, very pale yellow oil. The Polybutylketonwurde by infrared analysis be "* true *.

At s p- i e 1 4

In a 1 liter 4 neck reaction flask fitted with a The stirrer was fitted with 360 g of one as in example 2 produced polymer introduced. That, reaction ^ emic was warmed to Ziramer temperature and the hexane became partially removed under reduced pressure. 200 cc

• I

Acetic acid was added and, with vigorous stirring, 33 g (0.5 kol) zinc dust was added in small portions. There was an exothermic reaction which was maintained at a temperature of 35 ⁰ C by means of an 'ice bath. After the zinc had been completely added (45 minutes), the reaction mixture was heated to 60 G with a heating mantle and held at this temperature for 1 hour

009820/1672

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Transferred and the (soil) acetic acid residue was removed. The remaining product in hexane was in a 1 «liter 4-necked round bottom flask and added the hexane Removed reduced pressure, 200 cc of toluene was added and using a Dean Stark trap, those in the product remaining acetic acid and the mass removed. That Toluene was then removed under reduced pressure to isolate a very viscous light yellow oil. It was filtered by suction (using a heating lamp) to remove turbidity and form the polybutyl ketone, which was determined by infrared analysis, -.

Example 5

A 4-neck reaction flask equipped with a stirrer was charged with 250 g (0 * 193 mol) of a polybutyl ketone (molecular weight 1385) prepared as in Example 4, 12.1 g of tetraethylene pentamine (0.064 Hol) and 130 g of process oil . ^{The reaction mixture was heated to 150 0} O over a period of 5 hours under a 20 mm vacuum. Han allowed the reaction product to cool to room temperature. The mixture of compounds had a nitrogen analysis of $ 1.01.

009820/1672 _ ₂₁

Example 6 . '

A 4-necked reaction flask was charged with 35 g (0.02-6 mol) of polybutyl ketone, molecular weight 1350, 1.9 g of triethylenetetramine (0.013 mol) and 70 ml of toluene. The mixture was treated under reflux at 120 ⁰ C over a period of 4 hours, the water of reaction was removed. The 1,10-bis-polybutyl (1350) identriethylenetetramine was allowed to come to room temperature; it was covered with solvents. Infrared analysis indicated that 80 $ of the carbonyl had been removed - giving G = U. It was determined by analysis that there was $ 1.12 of nitrogen in the product. ,

The following products in Table I show additional examples of Schiff and to ship ^r see bases of the present invention. The name TAPA means tetraethylene pentamine. The bis-Schiff bases using a Ketan "in which the reaction - prepared (partner (c) is the same as the reactants (a).

00982Ö / 1672 ~ ²² ~

Polyolefin
(Molecular
Weight)
(a) Tabel I. 0: 0.0
0: 1.0 % Stick
material link at
game
No.' Polybutene
(1385)
Polybutene
(1385) Amih
(b) Mol- .. J
behaves
nis 1.95
1.40 1-polybutyl (1350) -
identetraethyl
enpentamine
1,13-bis (polybutyl-
(i35O) identetra- 7th
8th TlPA
TÄPA 1.0i1,
1.0: 1,

9 polybutene

(1385)

TÄPA 1.25: 1.0: 1.0 1.15

10 polybutene
(985)

TÄPA 2: 1: 1

ethylene pentamine

Manufactured according to the method described above Mixture of compounds

Mixture of compounds prepared by the process described above.

⁼ Are to which the novel compounds of this invention added to lubricants, especially lubricating oils which can be used as the base oils are, as far as the detergent action, not limited. Accordingly, lubricating oils based on haphthene, paraffin and other hydrocarbon bases can be used, as well as lubricating oils derived from carbon products and synthetic oils, such as alkylene polymers, alkylene oxide polymers, dicarboxylic acid esters, alkylated benzenes, silicate esters, silicone polymers and the like are suitable.

3S2Q / 1672

-25-

The Schiff’s bases and bis-Schlff’s bases of this invention can be used in lubricating oils * in amounts from about 0.05 percent by weight to about 25 percent by weight. Adhesive concentrates from $ 60 "to $ 95 are also contemplated. However, it has been found that in finished formulations, for most applications, anything from about 0.25 percent by weight to about 10 percent by weight is sufficient." the compounds of this invention may preferably in the aforementioned Kengen in fuels, particularly fuel oils and various LeichtprOduk- \

■ i

th gasoline, heating oils, etc. are also used 'as, WO-j also rin detergent- or Dipergierraittelwiriiung \ exhibit.

The effectiveness, with "which the Schiff * see bases and bis-Schiff" see bases of this invention impart low-temperature detergent properties, is illustrated by the results of a detergent test, which continues to be known as the "Lacquer deposit test" is referred to, [which consists in passing 3 gasoline (exhaust) gases through a sample of a preparation in a suitable container under controlled conditions and then aging the "sample in an oven. The extent of the deposits is then determined by washing the oil with hexane. At the same time, an experiment is carried out with a control preparation ^- mg. The amount of debris that exists when 009820/1 & 72

the test detergent used compared ^ u the amount on deposits that are present when no test detergent is used is recorded as the percentage reduction in deposit. This particular testing procedure is Relatively useful as it compares well with the results obtained in Lincoln MS Sequence 5 matches. Ifrrfcer using the above test procedures the results shown in Table II were obtained. In each test, 2 percent by weight of a

bond used according to this invention.

Table II

Additive paint deposit test

<fo reduction

Product of the example 3 0

Product of the example 4 13 Product of Example 5-90

Product of Example 6 80

Product of Example 7 86

Product of Example 8 84

Product of Example 9 86

These results, listed in Table II, demonstrate the effectiveness of the ship »see bases and up ship see Bases of this invention as detergents on * those obtained by using the * long-chain, ketones, examples 3 uriö 4,

009820/1672

•. ■ - ■■ "■." · "■■■ -25-

..; ■■■ Λ645Ο56:

• -25- ■ -:

These results show that there is only one oil solubility Polymerizats, with the content of a functional group »j does not give any detection property »;

Since the greater part of the commercially available oils have a large number of subject to tendencies of tendency, it is generally '; -necessary to have more than one 'type of additive in one end use lubricant preparation. So it is, although the above. produced reaction products are effective detergents, (| often necessary to use such products in conjunction with other types of additives such as metal-containing detergents and / or dispersants, corrosion inhibitors, extreme pressure additives, oxidation inhibitors, viscosity index improvers, lowers, anti-show agents and the like, to use «~"

While the present invention is described with reference to various specific examples and embodiments are described was, it is to be understood that the invention is not limited to this and can be varied in different ways in practice within the scope of the following claims,

-26-

Claims (1)

■ 16 * 5056 " _- - Λ -26- "- -" ■■■■■. -, '. - ^{i =} 'P ate nt an s ρ r ü ρ h et 1, lubricants and fuels with a content of detergents, characterized by the content of (a) one or more compounds of the general formula R - G = H - R ₁ - N 1 · Η, and or (b) one or more terbindungen of the general Formula = HC = K -R ₁ -N = C ^R 6 wherein R is a polymer of a lower olefin, where- the polymer has a molecular weight of approximately 500 to about 3000, R. a divalent alkyl en, phenylene, alky! phenylene, haloalkylene, halophenyrlene, a hydrocarbon chain of from 4 to 16 carbon Atoms and from 1 to 6 nitrogen atoms, where said hydrocarbon chain optionally from about 1 to 4 divalent radicals, namely piperazines, Contains phenylene and / or aminophenylene, and / or a substituted hydrocarbon chain, where the said substituted hydrocarbon ν 009820/1872 _27- material chain from 4 to 16, carbon atoms and from 1 to Contains 6 nitrogen atoms, and said substituent Alkyl, aminoalkyl, alkyl-amino-alkyl, dialkyl-aminoalkyl, N-piperazinoalkyl, alkyl-piperazino-alkyl and / or a hydrocarbon chain of from 4 to 8 carbon atoms and is from 1 to 3 nitrogen atoms, where the. said hydrocarbon chain optionally contains from about 2 to 4 piperazino residues, R „and Ε «identical or different and hydrogen, alkyl, aryl, Aralkyl, alkaryl, haloalkyl and / or haloaryl, R. R, hydrogen, alkyl, aryl ,. Aralkyl, alkaryl, Haloalkyl and / or haloaryl, Re hydrogen and / or or Alkyl, Rg En, hydrogen, alkyl, aryl, aralkyl, Can be haloalkyl and / or haloaryl. 2 · Lubricants and fuels in accordance with. Patent claim 1, characterized in that in a Schiff's base R is polybutyl with an average molar weight of about 7uO to / about 2COC. 3 * Lubricants and fuels according to patent claim 1, characterized in that in a ship area "base R polybutyl with a linear sinolecular weight of 70-10", R _{1 has} a hydrocarbon chain IAt B carbon atoms and 3 nitrogen atoms "a K < p3ilenwösser * fabric chain ü: it "€ is carbon atoms and 2 nitrogen atoms and / or phenols and R« and R, hydrogen 009820/1672 _ΛΟ . - ■ ". _..-. ■■ ■ ■" '. -28- are. 4. Lubricants and propellants geinäij claim 1, characterized in that in a bis-Schiff base R and R. are polybutyl with an average molecular weight of 700 Ms 2000, and R ₅ and Rg are alkyl with 1 to 4 carbon atoms. 5. Lubricants and fuels in accordance with; Patent claim 4, characterized in that «; in a bis-Schiff base R _{1 is} a hydrocarbon chain with 8 carbon atoms and • 3 nitrogen atoms and / or a hydrocarbon chain with 6 carbon atoms and 2 nitrogen atoms. 6. Process for the manufacture of see bases of the ship general formula R - C = N - R ₁ -H ₅ and from bis Schiff's see bases of the general formula ■ R - 0 = N - R ₁ - Ή = G
1 -ν ^E 6 wherein the substituents R to R ^ have the following meaning have characterized by the implementation . 1S45Ö56 -29- (a) a compound ,, of the general formula 0
η R- C- B- wherein R is a polymer of a lower olefin having a molecular weight of about 500 to about 3000 and R, -, hydrogen and / or alkyl, with Cb) a compound of the general formula I. did ♦ wherein R _{1 is} a hydrocarbon chain with from 4 to 16 carbon atoms and from 1 to 6 nitrogen atoms, provided that at least 1 nitrogen atom within R. is substituted with at least 1 hydrogen atom, said hydrocarbon chain optionally from 1 to 4 divalent piperazino and / or Contains phenylene radicals and / or is a substituted hydrocarbon chain, said substituted hydrocarbon chain containing from 4 to 16 carbon atoms and from 1 to 6 nitrogen atoms and said substituent being alkyl, aminoalkyl, alkyl-amino-alkyl, dialkyl-aminoalkyl, N- piperazino-alkyl, alkyl-piperazino-alkyl and / or a hydrocarbon chain with 4 to 5 carbon atoms and from 1 to 3 nitrogen atoms, said hydrocarbon chain optionally containing from 2 to 4 piperazino radicals, and * ö Ö 9 8 2 Ö / 1 0 7 2 ί '-30- -'
(ο ·) a compound of the general formula 0
R ₄ -G where R. R, Yfeaa, alkyl, aryl, aralkyl, alkaryl, haloalkyl and / or haloaryl and "Rg R ₅ , hydrogen, alkyl, aryl, aralkyl, alkaryl, haloalkyl and / or haloaryl can be in a molar ratio of the sum of ( a) iilus (c) to (b) from about 2.1: 1 to about 4: 1, provided that '·' is at least 1 mole (a) and 1 mole (e) per mole (b), at one temperature of about 50 ⁰ C to about 300 ° C.