DE1268299B - Lubricating oil - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Number:
File number:
Registration date:
Display day:

ClOm

German AI .: 23c - 1/01

1268299
P 12 68 299.4-43
August 16, 1962
May 16, 1968

N-dialkylaminoalkylalkenylsuccinic acid esters and Are N-polyalkyleneaminekenylsuccinic acid imides known as a detergent for lubricating oils. Bisphenols are also known as lubricating oil additives.

However, these individual components have the disadvantage that they are at high temperatures, such as these z. B. occur in internal combustion engines, tend to precipitate.

The invention now relates to a lubricating oil consisting of a mineral or synthetic one oil and a combination of two individual components known as lubricating oil additives, and optionally other common additives, which is characterized in that it is an alkyl or Alkylenesuccinic acid amide of the general formula

R-CH Cs

N - [<R,) _X -NH], -.

CH,

Il ο

L- (R ₁ ^ -N

Lubricating oil

Applicant:

"Shell" Research Limited, London

Representative:

Dr. E. Jung, patent attorney,
8000 Munich 23, Siegesstr. 26th

Named as inventor:

George Nacson,

Queen's Park, Chester (Great Britain);

Gedeminas Joseph Reinis, Edwardsville, JlI .;

Bobby Malone, East Alton, JIl. (V. St. A.)

Claimed priority:

Great Britain August 18, 1961 (29 984),

dated July 2, 1962
V. St. v. America April 19, 1962 (188902)

where R is a polyalkyl or polyalkylene radical having 20 to 500 carbon atoms, Ri is a CHo group, .γ and ζ 1 to 3, y0 to 6 and R2 is a hydrogen atom or a Q 5 -alkyl radical, or the two radicals R2 are a heterocyclic ring of the structure

CH-R

- N

CH,

form, in which R has the above meaning, and a bisphenol of the general formula

_0H

wherein R ^{1 is} a Ci m-alkyl radical, m is 1 to 4 and X is a CHi group or sulfur.

R is preferably a polymer of an alkene with 2 to 8, in particular with 2 to 5 carbon atoms, in which the polymer has a molecular weight of 300 to 5000, in particular 800 to 1500.

The number of carbon atoms in the R group is preferably 30 to 200. Examples of such Polymers are: polyethylene, polypropylene, polybutylene, polyisobutylene, ethylene-propylene copolymer, Ethylene - isobutylene - copolymer

and ethylene-α-methylstyrene copolymer.
Preferably jc and ζ have the value 1.
When y is 0, Ri is preferably an ethylene, propylene or butylene radical, and R2 is preferably methyl, ethyl, propyl or butyl radicals. It is particularly preferred that Ri contain 2 or 3 carbon atoms and each R2 contain 1 carbon atom. If y has the value 1 or a higher value, this number is preferably 1 to 6 and particularly preferably 3. In this case, Ri is preferably an ethylene radical, and the R »are preferably hydrogen atoms (monosuccinic acid imide), or they form a heterocyclic ring, as above

M »549/379

3 4

described (disuccinic acid imide). Mixtures of phenyl) methane, bis (2,6 - tert-butyl - 4 - hydroxy

two or more additives, e.g. B. of mono- and phenyl) methane, bis- (3,5-ditert.octyl-4-hydroxy-

Diimides can be used to advantage. phenyl) methane, bis (3 - tert.butyl - 5 - tert.octyl-

The succinimide is prepared by known processes, 4-hydroxyphenyl) methane and especially bis (3,5-di). 5 tert-butyl-4-hydroxyphenyl) methane.

In order to form disuccinic acid imides, the bisphenols are prepared by known processes

the R.2 radicals of these amines are hydrogen. manufactured.

Examples of such amines are: «, ^ - primary poly- Further common lubricating oil additives can be used

amines, such as ethylenediamine, diethylenetriamine, tri-lubricating oil according to the invention are added, ethylene tetramine, propylenediamine, butylenediamine, tri-io e.g. alkyl, cycloalkyl, alkaryl, aralkyl and

methyltrimethylenediamine, tetramethylenediamine, di-aryl phosphites, phosphates, phosphonates and their

aminopentene, pentamethylenediamine, diaminohexane, thio derivatives, such as Ca ls-alkyl phosphites, e.g. B. Di-

Hexamethylenediamine, heptamethylenediamine, di- and tributyl-, -octyl-, -Iauryl-, -stearyl-, -cyclohexyl-,

aminooctane, decamethylenediamine and the higher benzyl, cresyl, phenyl phosphites or phosphates Homologues up to 18 carbon atoms. 15 and their thio derivatives; PoSrrTerpene reaction pro-

In the manufacture of monosuccinic acid products; Organophosphates, such as dibutyl methane phosphates

imides, amides and salts can contain the same phonate, dibutyltrichloromethane phosphonate, dibutyl

Amines are used, or substituted monochloromethane phosphonate and dibutyl chlorobenzene

ated amines are used, such as N-methyl zolphosphonate. The esters of acids of the pentavalent

ethylenediamine, N - ethylethylenediamine, N - propyl 20 phosphorus, such as diphenyl, dicresyl, triphenyl,

ethylenediamine, N-2-hydroxypropylethylenediamine, tricresyl, trilauryl and tristearyl phosphate, P2S5-

Penta- (l-methylpropylene) -heptamine, di- (I-methyl terpene reaction products and their mixtures,

butylene) - triamine, pentaamylene hexamine, tri- These additives are each in an amount of

(1,2,2-trimethylethylene) tetramine, di- (I-methyl- 0.1 to 10, preferably 0.25 to 5 percent by weight

amylene) -hexamine, di- (1,3-dimethylpropylene) -pent-25 added.

amine, penta- (l, 5-dimethylamylene) hexamine, di- The lubricating oil according to the invention can also

(1-methyl-4-ethylbutylene) -triamine, penta- (1,2-di- and other additives are added; e.g.

methyl -1 - isopropylethylene) - hexamine and tetra- anti-seizure agents, anti-foaming agents,

octylenepentamine. z. B. silicone polymers; Improvers for the

The amines are viscosity index 30, z. B. polymeric acrylic acid esters;

manufactured. Extreme pressure additives, ζ. B. dibenzyl disulfide; Rust-

The bisphenols can prevent one to eight alkyl groups, e.g. B. the condensation product

contain. However, they preferably have two to three maleic anhydride and long chain olefins;

six alkyl groups. Bisphenols with four alkyl oil improvers, e.g. B. acidic

groups are particularly preferred. Each of these 35 free sebum; as well as surfactants, e.g. B.

Alkyl groups can have 1 to 10 carbon atoms, pre-peroxidized aromatic extracts, preferably 2 to 6 carbon atoms and especially

suitably contain 4 carbon atoms. In addition to the production of disuccinic acid imides the alkyl groups contained in any particular bisphenol may be the same or different be divorced and can be primary, secondary or

be tertiary alkyl groups. Bisphenols, the min- polyisobutylene with a molecular weight of 1185

at least one tertiary alkyl group and a bromine number of 21 was heated to 100 C.

particularly preferred. and an equivalent amount of maleic anhydride

Examples of such bisphenols are: Bis- (3-ethyl-45 added slowly in the course of about 30 minutes.

4-hydroxyphenyl) disulfide, bis- (3-methyl-4-propyl- The reaction mixture was heated to 199-204 ° C

5-hydroxyphenyl) disulfide, bis- (2-isopropyl-3-butyl- heated and 16 hours at this temperature

5-hydroxyphenyl) selenide, 2,2'-diethyl-3-tert-butyl. On cooling, mono- (polyiso-

4: 4'-dihydroxydiphenyIseIenid, bis-1,2- (2: 6-di-tert-butylene) -succinic anhydride by dissolving in

butyl-4-hydroxyphenyl) thiaethane, bis-l, 2- (2: 5-di- 50 1.51 light petroleum (boiling range 60 to 80 C) and

isopropyl-3-hydroxyphenyD-thiaethane, bis- (3: 5-di- separation of the product obtained by filtration,

tert-butyl-4-hydroxyphenyl) sulfide, 2,4-diisobutyl- About 2 moles of this product were with 1 mole

3-hydroxybenzyl-2 ¹ , 4 ¹ -dipropyl-3 ¹ -hydroxybenzyl-tetraethylene pentamine and mixed into a solution

sulfide. Bis-1,2- (3-octyl-5-tert-butyl-4-hydroxy- in light petroleum) was added

phenyl) ethane, bis-l, l- (2,6-diisopropyl-4-hydroxy- 55 distilled off and replaced by 1 l of toluene, which is also

phenyl) ethane, l, 2-bis (2,4-ditert.pentyl-3-hydroxy- if distilled off to azeotrope the water

phenyl) propane, bis-2,2- (4,5-di-tert-butyl-2-hydroxy-. The residue was increased to 199 bis

phenyl) propane, bis (2 - tert-butyl - 2 - isopentyl- 204 C and heated at this temperature for 3 hours

4-hydroxyphenyl) amine, bis (3,5-dibutyl-4-hydroxy- held. The isolated product.

phenyl) ether, bis (2,6-dipropyl-4-hydroxyphesiyl) - 60 amine diimide of mono- (polyisobutylene) amber

ether, bis (2,5-dipentyl-4-hydroxyphenyl) sulfide. acid, was soluble in oil and showed excellent

Bis - (2,5 - dihexyl - 3 - hydroxyphenyl) sulfide. Bis-cleaning properties. (2 - methyl - 5 - tert-butyl - 4 - hydroxyphenyl) sulfide.

Bis- (2-methyl-5-tert-butyl-6-hydroxyphenyl) sulfide Example 2 and especially bis- (3-tert-butyl-5-methyl-2-hydroxy-65

phenyl) sulfide. Examples of bisphenols with about 0.45 moles of tetraethylene pentamine and 1 mole

Methylene bridges are: bis (2,3-ditert.butyl-4-hydroxy- des essentially below those in Example 1

phenyl) methane, bis (2,5-di-tert-butyl-4-hydroxy- mono- (poly-

butenyl) succinic anhydride were mixed with stirring in a nitrogen atmosphere at 52 ° C. The temperature was increased to 177 C over the course of an hour, whereupon the absolute pressure during Was lowered to about 200 torr for 30 minutes to remove the water. Then you left that Cool the reaction mixture to room temperature at the said reduced pressure.

Example 3

About 1 mol of mono- (polybutenyl) succinic anhydride from Example 2 was treated with about 0.5 mol of triethylenetetramine under the reaction conditions of Example 2 reacted and a final product as identified above obtained which was oil soluble and had excellent cleaning properties.

example

Olefin to succinic anhydride

Polyisobutylene (molecular weight 850) to succinic anhydride

Polyisobutylene (molecular weight 850) to succinic anhydride

Polyethylene isobutylene (molecular weight 1000) to succinic anhydride

Polyethylene-u-methylstyrene (Molar weight 800) to succinic anhydride

Polyisobutylene (molecular weight 1000) to succinic anhydride

Polyisobutylene (molecular weight 1500) to succinic anhydride

Polypropylene-polyisobutylene (molecular weight 3000) to succinic anhydride

Diethylenetriamine

M, f> j-pentamethylenediamine

Tetraethylene pentamine

Tetraethylene pen tamin

methylenediamine

f /, f) -butylenediamine

Tetraethylene pentamine

Preparation of monosuccinic acid imides Example 11

About 0.5 moles of mono- (polyisobutylene) succinic anhydride. whose polyisobutylene radical has a molecular weight 615 and a bromine number 21, was with 1.0 mol of tetraethylene pentamine in light gasoline solution reacted at 177 to 216 C for about 20 hours. The light petroleum was distilled off and replaced by 1 l of toluene, which is then also distilled off for the purpose of azeotropic removal of the water became. The residue was heated to 199-204 ° C. and kept at this temperature for 3 hours. The end product was an oil-soluble tetraethylene pentamine monoimide of mono- (polyisobutylene ^ succinic acid.

Example 12

84 grams (0.45 moles) of N-dipropyl tetraethylene pentamine and 702 grams (0.45 moles) of the mono- (polybutylene) succinic anhydride described above according to example 2 was carried out with stirring at 52 ° C. in a nitrogen atmosphere mixed. The temperature was increased to 204 ° C. over the course of an hour, whereupon the absolute pressure was reduced to about 200 torr over 30 minutes to remove the Water to facilitate. Then the reac-2: 1 was left

2: 1

2: 1

2: 1

2: 1

3: 1

3: 1

temperature
C.

204

177

191

177

177

204

204

End product

Diethylenetriamine diimide of mono- (polyisobutylene) succinic acid

Pentamethylene diamine bis (polyisobutylene succinic acid imide)

Tetraethylene pentamine diimide of mono- (polyethylene-isobutylene) succinic acid

Tetraethylene pentamine diimide of mono- (polyethylene-methylstyrene) succinic acid

Hexamethylene diamine bis (polyisobutylene succinic acid imide)

Butylenediamine bis (polyisobutylenesuccinic acid imide)

Tetraethylene pentamine diimide of mono- (polypropylene polyisobutylene) succinic acid

Cooling mixture at this reduced pressure to room temperature.

Example 13

The procedure was as in Example 12 with the exception that dimethylaminopropylamine in the reaction mixture was used and the molar ratio of the polyamine to the anhydride was about 1: 1. The end product is an N-dimethylpropylalkenyl succinic acid imide.

Preparation of hemiamides Example 14

By reacting a polyisobutylene (molecular weight 850) with succinic anhydride at about 204 C, as in Example 1, polyisobutylene succinic anhydride was prepared. About 500 g of the polyisobutylenesuccinic anhydride thus obtained were treated with 50 g of diethylenetriamine in toluene Mixed at room temperature. The amine was added in portions and the temperature became so regulated that it did not rise above about 49 ° C. the Reaction proceeded in 15-30 minutes after which the solvent was removed and the final product isolated became.

Further examples of monosuccinic acid imides:

example Olefin to succinic anhydride Amine Mole
relationship temperature
C. Type of end product 15th Polyisobutylene (molecular weight 850) N-diethylamine propyl 1: 1 216 Imide to succinic anhydride amine 16 Polyisobutylene (molecular weight 850) N-methyltetraethylene 1.5: 1 49 Hemiamide to succinic anhydride pentamine 17th Polyethylene isobutylene (Mol N-dimethylamine 1: 1 232 Imide weight 1000) to amber propylamine acid anhydride 18th Polyethylene-a-methylstyrene (Mol N-diethylmethyl- 1: 1 232 Imide weight 800) to succinic acid
Anfivdrid aminoheptylamine 19th Polyisobutylene (molecular weight 1000) N-dimethylethylene 1: 1 49 Amide amine salt to succinic anhydride diamine 20th Polyethylene-propylene to Bern N-dimethyl diethylene 1: 1 221 Imide stinic anhydride triamine

40

45

Mixtures of imides and of one or more imides and their salts are advantageous used. The proportions between the components can be within wide limits be changed, e.g. B. from 10:90 to 90:10. Examples of such mixtures can be given become: (1) 80% Example 1 and 20% Example 11; (2) 80% Example 11 and 20% Example 2; (3) 90% Example 12 and 10% Example 2; (4) 80% Example 1 and 20% Example 13; (5) 70% example 7 and 30% Example 16; (6) 50% example 1 and 50% example 19.

To further illustrate the invention, the lubricating oil mixtures given below were used manufactured and tested. The percentages are based on weight.

Mixture A

Addition according to example 1 2%

Bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -

methane 0.5%

Mineral lubricating oil (SAE 20) .. 97.5%

Mixture B

Addition according to example 2 2%

Bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -

methane 0.75%

Mineral lubricating oil (SAE 20) .. 97.25%

Mixture C

Addition according to example 2 2%

Addition according to Example 12 0.5 ⁰ O

Bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -

sulfide 0.75 "/ ,,

Mineral lubricating oil (SAE 20) .. 96.75%

Mixture D

Addition according to example 4 2%

Addition according to example 14 0.5%

Bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -

methane 0.75 "/ ,,

Mineral lubricating oil

(SAE 20 W-30) 96.75%

55

60 mixture E

Addition according to example 1 2%

Addition according to example 12 0.5%

Bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -

methane 0.75 ° / »

Tricresyl phosphate 0.5%

Mineral lubricating oil (SAE 20) .. 96.25%

Mixture F

Addition according to example 1 2%

Addition according to example 11 0.5%

Bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -

methane 0.75%

Tricresyl phosphate 0.5%

Mineral lubricating oil (SAE 20) .. 96.25%

Mixture G

Addition according to Example 4 0.2 "'o

Addition according to example 11 1 "'0

Bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -

methane 0.75%

Tricresyl phosphate 0.5%

Mineral lubricating oil (SAE 20) .. 96.25%

Mixture H

Addition according to example 1 0.3%

Addition according to Example 12 2.5'Vo

Bis- (3,5-ditert.butyI-4-hydroxyphenyl) -

methane 0.75%

Tricresyl phosphate 0.80%

Dicresyl phosphate 0.04%

Mineral lubricating oil

(SAE 10 W-30) 95.65 ⁰ A,

Mixture .1

Addition according to example 11 2 "/«

Bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -

methane 0.75%

Tricresyl phosphate 0.5%

Mineral lubricating oil (SAE 20) .. 96.75%

These mixtures were tested under various laboratory and practical engine conditions checked.

Hot plate test

A plate 12 inches long and 2.5 inches wide is along the narrow side at the top and bottom Provide end with channels for the distribution and for the collection of oil. The plate is on Heated 270 C and kept at this temperature, 500 g of lubricating oil is allowed for 6 hours over the Circulate the plate while maintaining a flow rate of about 6.5 cc per minute. After completion of the test, the precipitates are scraped off the plate and washed with petroleum ether (Boiling point 60 to 80 C) rinsed into a sintered glass filter crucible. After thorough washing with Petroleum ether, the precipitate is dried at 100 ° C. and weighed after cooling.

The test was conducted using Mixture J and a variety of lubricating oil mixtures carried out for comparison purposes. The results are summarized in the following table.

Hot plate test Precipitation Base oil additive amount in g 198.4 SAE 20 2 ¹ Vo according to example 11 182.0 SAE 20 0.75% AN 2 * 125 SAE 20 0.75% AN 2 * + 0.75% TTP ** 31.4 SAE 20 2 "/ ο according to example 11 + 0.75% AN 2 * 3.8 SAE 20 Mixture J 14.4 SAE 20 1 ⁰ Ai according to example 11 + 0.75% AN 2 * + 0.5% TTP ** 98.0 SAE 20 4.5% commercially available Mixed polymer Lauryl methacrylate and N-vinyl pyrrolidone 77.2 SAE 20 4.5% commercially available Mixed polymer Lauryl methacrylate and N-vinyl pyrrolidone + 0.75% AN 2 *

35

40

45

¹ bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane.
'Tritolyl or tricresyl phosphate.

10

Claims (1)

Claim: Lubricating oil, consisting of a mineral or synthetic oil and a combination of two individual components known as lubricating oil additives and, if necessary, other customary ones Additives, characterized in that it is an alkyl or alkylene succinic acid imide the general formula R-CH wherein R is a polyalkyl or polyalkylene radical with 20 to 500 carbon atoms, Ri is a CH ₂ group, χ and ζ 1 to 3, y 0 to 6 and Rg is a hydrogen atom or a Ci 5 -alkyl radical, or the two radicals R2 are a heterocyclic ring the structure - N CH-R
CH ₂ Il form, in which R has the above meaning, and a bisphenol of the general formula HO OH wherein R ^{1 is} a Ci -10 -alkyl radical, m is 1 to 4 and X is a CH2 group or sulfur. Considered publications:
British Patent No. 884 164. 809 549/379 5.6 »Q Bundeadruckerei Berlin