DE1257330B - Lubricating oil - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

ClOm

C 1OM 169/00 B 48

German KL: 23 c -1/01

Number:
File number:
Registration date:
Display day:

1 257 330
S 87855IV c / 23 c
October 14, 1963
December 28, 1967

The use of alkyl or alkenyl substituted succinic acid imides, amides or amine salts is known as lubricating oil additives. These compounds are good detergents, however own they do not have sufficient stability and insufficient wear-preventing properties under extreme pressure conditions Properties and show no resistance to sludge formation and corrosion. Antimony or dithiocarbamates and bisphenols are also known as lubricating oil additives.

The invention now relates to a lubricating oil containing a mixture individually as lubricating oil additives known compounds, which is characterized in that it is a mixture of

a) a C ₂₀ _ ₅₀₀ alkylene or alkyl-succinimide or -aminsalz amide of an optionally substituted alkylene or Arylenpolyamins,

b) an antimony thiocarbamate or dithiocarbamate of the formula

Il

'N - C - X - Sb

wherein R is aliphatic or aromatic hydrocarbon radicals with 4 to 18 carbon atoms, X is oxygen or sulfur, at least one X being sulfur, and

c) optionally an alkylated bisphenol of the formula

OH

OH

wherein YS, O, Se or an S - S-, S - CH ₂ -, CH ₂ - S-CH ₂ -, CH (CH ₃ ) -, CH (C ₂ H ₅ ) -, C (CH ₃ ) ₈ -, C (C ₂ H ₅ V, (means CHA-3 or NH group.

Surprisingly, it has been found that by combining the above-mentioned lubricating oil additives a synergistic improvement in the properties of the individual lubricating oil additives occurs

The additive a) has a straight-chain or branched alkylene or alkyl radical, which is of olefins having 2 to 8 carbon atoms, such as ethylene, propylene, butene-1, isobutene, hexene-1 or Styrene, derived in the form of a homopolymer or copolymer, and 20 to 500 carbon lubricating oil

Applicant:

Shell International Research

Maatschappij N.V., The Hague

Representative:

Dr. E. Jung, patent attorney,

Munich 23, Siegesstr. 26th

Named as inventor:

Roland Frederick Bergstrom,

Martinez, Calif .;

Hyman Ratner, Florissant, Mon. (V. St. A.)

Claimed priority:
V. St. v. America October 15, 1962
(230756)

contains atoms and a molecular weight, measured by the light scattering method, from 300 to 5000, preferably from 800 to 1500.

Examples of such polymers are polyethylene, polypropylene, polybutene, polyisobutylene and copolymers from ethylene and propylene, from ethylene and isobutylene and from ethylene and a-methylstyrene.

It is known that alkylsuccinic anhydride is prepared by monoalkylation of Maleic anhydride with the olefin polymers described by customary methods.

The optionally substituted alkylene or arylene polyamines used to form the amine salts can use the general formula

: NO'). - NH] ₂ , - (R ') * - NH ₂

have, in which R _{1 is} hydrogen or Qe-alkyl radicals and / or aryl radicals, which can be identical or different, while R 'is an alkylene radical having 1 to 8, preferably 1 to 4 carbon atoms or a Cx-4-alkylated phenylene or Naphthylene radical, and where χ is a number from 0 to 8, y is a number from 0 to 5 and ζ is a number from 1 to 18. Suitable amines are, for example: Alkylenepolyamines, such as ethylenediamine, diethylenetriamine, tri-

709 710/533

Ethylenetetramine, 1 - methylethylenediamine, 1 - ethylethylenediamine, Propylenediamine, butylenediamine, trimethyl - trimethylenediamine, tetramethylenediamine, Pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, Decamethylenediamine and higher homologues with up to] 8 carbon atoms; also phenylenediamine, alkylated phenylenediamines with methyl, ethyl, propyl or butyl groups as core substituents as well as naphthylenediamine and alkylated naphthylenediamines. Also Ν, Ν'-dimethylethylenediamine, N, N '- diethylethylenediamine, N, N' - dipropylethylenediamine, N, N '- di - (2 - hydroxypropyl) - ethylenediamine and the corresponding propylene and butylenediamines, Penta - (1 - methylpropylene) - hexamine, tetrabutylene pentamine, hexa - (1,1 - dimethylethylene) - heptamine, Di- (I-methylbutylene) triamine, pentaamylene hexamine, Tri - (1,2,2 - trimethylethylene) - tetramine, di- (I-methylamylene) - triamine, tetra - (1,3 -dimethylpropylene) - pentamine, penta - (1,5 - dknethylamylen) - hexamine, di- (I-methyl - 4 - ethylbutylene) - triamine, Penta - (1,2 - dimethyl - 1 - isopropylethylene) hexamine and tetraoctylene pentamine are suitable.

The polyalkylenepolyamines in question are prepared by known processes. Preferred polyamines are the ethylene amines, such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, N - dimethylaminopropylamine, N - dimethylaminobutylamine, N - diethylaminopropylamine and methylpropylaminoamylamine.

The desired imides, amides or amine salts are preferably prepared at a molar ratio of the polyamine to succinic anhydride between 0.1: 1 and 1: 1. The reaction temperature for the formation of imides or amides is between 104 and 260 ° C, preferably between 149 and 232 ° C, for the formation of atnine salts between room temperature and 149 ° C, preferably between 38 and 149 ° C.

example 1

250 g of a polyisobutylene with a molecular weight of 615 and a bromine number of 21 were ^{heated to 100 °} C. and 30 g of maleic anhydride were slowly added over the course of 30 minutes. The reaction mixture was then heated ^{to 199-204 ° C. for 4 hours.} The reaction mixture was then ^{heated to 277 °} C. for a further 16 hours. After cooling, the reaction mixture in 1.51 petroleum ether was dissolved and having a boiling point of 60 to 8O ⁰ C the solution filtered. 19 g of tetraethylene pentamine were added to this solution, the solvent was distilled off and replaced by 11 toluene. The toluene was distilled off from the solution to remove water. The residue was ^{heated to 199-204 °} C. for 3 hours.

Example 2

From 1000 g (1 mol) of a polybutene with a molecular weight of about 1000 and 98 g (1 mol) Maleic anhydride became polybutenyl succinic anhydride with a saponification index of 79 manufactured.

702 g (0.45 mol) of the polybutenylsuccinic anhydride were mixed with 84 g (0.45 mol) of tetraethylene pentamine converted to a succinic acid imide.

Example 3

21.3 g (0.21 mol) of dimethylaminopropylamine and 150 g (1.09 mol) of that prepared according to Example 2 Polybutenyl succinic anhydride were converted to N-dimethylamine opropylalkenyl succinic acid imide.

Example 4

A polyisobutylene succinic anhydride has been made from a polyisobutylene having a molecular weight manufactured by 850 and maleic anhydride. About 500 g of this compound were at room temperature reacted with 50 g of diethylenetriamine to form a hemiamide.

Further examples of additives according to the invention are given below, specifying the ones used Reaction partners and the reaction conditions compiled.

Olefin succinic anhydride Amine Mole
relationship temperature
⁰ C Type of end product 5 Polyisobutylene Diethylaminopropylamine 1: 1 216 Imide (Molecular weight 850) 6th Polyisobutylene Tetraethylene pentamine 1.5: 1 49 Hemiamide (Molecular weight 850) 7th Polyethylene / isobutylene Dimethylaminopropylamine 1: 1 232 Imide (Molecular weight 1000) δ Polyethylene / a-methylstyrene Tetraethylene pentamine 1: 1 232 Imide (Molecular weight 800) 9 Polyisobutylene Tetraethylene pentamine 1: 1 49 Amine salt of polyiso- (Molecular weight 1000) succinic acid anhydrides

The additives of type a) are the lubricating oils in proportions by weight between 0.1 and 10 percent by weight, preferably between 0.25 and 5 percent by weight, based on the weight of the lubricating oil.

Compounds of the general formula are used as antimony thiocarbamates or antimony biocarbamates

N-C-X-Sb

used, wherein alkyl, aryl, aralkyl, alkaryl or Cycloalkyl radicals, which can be the same or different, and have at least 4 carbon atoms, preferably Have 8 to 18 carbon atoms, and X is sulfur or oxygen, where at least a remainder X must be sulfur. R are preferably alkyl radicals, in particular Q-io radicals, such as methyl, Ethyl-; Propyl, butyl or octyl radicals. R are too Phenyl, naphthyl, benzyl or cyclohexyl radicals. The following compounds are mentioned as examples: Antimony - diethyldithiocarbamate, antimony - dibutyldithiocarbamate, antimony - diamyldithiocarbamate, antimony - dibenzyldithiocarbamate, antimony - diphenyldithiocarbamate and antimony dicyclohexyldithiocarbamate.

A part of the antimony thiocarbamate, preferably 10 to 50 percent by weight, can be replaced by an alkyd Bisphenol of the general formula

HO

OH

wherein YS, O, Se or an S-S-, S-CH ₂ -, CH ₃ -S-CH ₂ -, CH (CH ₃ ) -, CH (C ₈ H ₅ ) -, C (CH ₃ ) _a -, C (C ₂ Hs) ₂ -, (CHa) ₁ -S- or NH- group. Alkylated bisphenols with a sulfur or a methylene bridge are preferred.

The alkylated bisphenols contain 1 to 8 alkyl radicals, preferably those with 2 to 6 alkyl radicals, in particular alkylated with 4 alkyl radicals. The alkyl radicals have 1 to 10, preferably 2 to 6, carbon atoms and especially 4 carbon atoms. The alkyl radicals of the selected bisphenol are the same or different and primary, secondary or tertiary alkyl radicals. Bisphenols with at least one tertiary Alkyl radicals are particularly preferred.

Examples of bisphenols are: bis (3-ethyl-4-hydroxyphenyl) disulfide, bis (3 - methyl - propyl-5-hydroxyphenyl) disulfide, bis - (2 - isopropyl - 3 - butyl - 5 - hydroxyphenyl) - selenide, bis -1,2 - (2,6 - ditert.-butyl -A- hydroxyphenyl) - thiaethane, bis -1,2 - (3 - octyl - 5 - tert - butyl - 4 - hydroxyphenyl) - ethane , 1,2 - bis - (2,4 - di - tert - pentyl - 3 - hydroxyphenyl) propane, bis (2 - tert - butyl - 5 - isopentyl - 4 - hydroxyphenyl) amine, bis - ( 3,5 - dibutyl - 4 - hydroxyphenyl) ether, bis (2,6 - dipropyl - 4 - hydroxyphenyl) ether; Bis- (2,5 - dipentyl - 4 - hydroxyphenyl) sulfide, bis (2 - methyl - 5 - tert-butyl - 4 - hydroxyphenyl) -suMd and especially bis (3-tert-butyl-5 - methyl - 2 - hydroxyphenyl) sulfide; Bis - (2,3 - di-tert-butyl -A- hydroxyphenyl) - methane, bis - (2,5 - di-tert-butyl -A- hydroxyphenyl) - methane, bis - (2,6 - di-tert-butyl - 4-hydroxyphenyl) methane and in particular bis (3,5-di-tert-butyl-hydroxyphenyl) methane.

The additives of type b) and the bisphenols are each used in concentrations of 0.05 to 10 percent by weight and preferably from 0.1 to 5 percent by weight based on the weight of the lubricating oil, added.

Naphthenic or paraffinic or mixed-base hydrocarbon oils are used as lubricating oils or synthetic oils are used.

Mixture A

Additive from example 1 4%

Antimony diamyldithiocarbamate 0.5%

Mineral lubricating oil (SAE 20) rest

Mixture B

Additive of example 2 4%

Antimony diamyldithiocarbamate 0.5%

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

methane 0.3%

Mineral lubricating oil (SAE 20) rest

Mixture C

. Additive of example 3 2%

Antimony dibutyldithiocarbamate 0.5%

ίο bis (3,5-di-tert-butyl-4-hydroxyphenyl) -

methane 0.3%

Mineral lubricating oil (SAE 20) rest

Mixture D

Additive of Example 4 5%

Antimony dibenzyldithiocarbamate 0.5%

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

methane 0.2%

Mineral lubricating oil (SAE 20 W-30) rest

Mixture E

Additive from example 1 4%

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

methane 0.2%

Antimony diamyldithiocarbamate 0.5%

Mineral lubricating oil remainder

he mixture F

Additive from example 1 1.5%

Antimony diamyldithiocarbamate 0.25%

Phenyl - «- naphthylamine 0.07%

Mineral lubricating oil (SAE 20) rest

The following tests were carried out:

Type of attempt

I. Thorn oxidation test (cf.
“Nat. Petr. News «
from September 17, 1941,
Pp. 294 to 296).

H. Sinclair oxidation test (cf.
ASTM-D-665-47T).

III. Caterpillar Diesel Paint Formation Test,
equivalent to that
Caterpillar L-1 diesel test with the
Modifications (A)
and (B).

IV. Induction periods
according to the thorn oxidation test
(see I) and the
Blotter spot test

(See U.S. Patent 2770530).

Test conditions

Temperature: 149 ⁰ C; Catalyst: Fe. The hours required to absorb 1500 ml of O ₂ are measured.

The mixture is allowed by the test oil at a temperature of 140.6 ⁰ C in the presence of Cu - Pb metal strips bubbled oxygen.

A) Fuel: odorless luminous oil. It will be the hours up to the observed Paint formation measured.

B) Fuel: natural diesel oil; Evaluation as under (A).

Temperature: 177 ° C; Passing air at one speed of 30ml / min .; Catalyst: Cu — Fe (20 parts per million each). The induction period (first numerical value) and the service life according to the blotter spot (second numerical value) measured in minutes.

Test results base oil: mineral lubricating oil

Examined mixture

1.11

hours

Cu-Pb weight loss

mg insoluble high

Viscose

sity ι J _n increase ι p _en tan {weight ·% I percent hours

ΠΙ

Paint- ! Overall education I worth

IV

Minutes

3.5 1.9

Mixture B 46.7 1.3

Mixture C 33.7 3.3

Mixture A

Mixture A

Mixture F

X = mineral oil (SAE 20) + 4 ° / ₀

Polymer from Example II 3.5! 301! 144

Y = mineral oil (SAE 20) + 0.5%

Zinc diamyl dithiocarbamate 22.4

Z = mineral oil (SAE 20) + 5 "/" polymer from Example II ■ + ■ 0.5% bis- (3,5-di-tert-butyl-4-hydroxy-

phenyl) methane 20.6 487:

XX = mineral oil (SAE 20) f 3%

Copolymer of vinylpyrrolidone - lauryl methacrylate 4- 1% bis (3,5-di-tert-butyl-4-hydroxy-

phenyl) methane

It is surprising that the antimony thiocarbamate known as an antioxidant is mixed with component a) improved corrosion and wear properties, as can be seen in the table, causes. This effect is achieved without adversely affecting the cleaning effect of the succinic acid derivative achieved. The cleaning effect of the lubricating oil according to the invention far exceeds that of a well-known and proven lubricating oil. It is known that polymeric detergents and antioxidants often adversely affect one another

The lubricating oils according to the invention can also contain other known additives, for example, anti-seizing agents, anti-foaming agents such as silicone polymers, agents for Improvement of the viscosity index, such as polymeric acrylic acid esters, extreme pressure additives such as dibenzyl disulfide, Rust inhibitors, such as sorbitan monooleate or butyl stearate, agents for improving the oily, such as acid-free tallow or oleic acid, amines, such as phenyl -% - naphthylamine, N, N'-di-sec-butyldiaminophenyloxyd or octadecylamine.

Claims (1)

Patent claims: 1.Lubricating oil, containing a mixture of compounds known individually as lubricating oil additives, characterized in that it is a mixture of a) a C ₂₀ _ _B0O alkylene or alkyl substituted succinic acid imide, amide or amine salt of an optionally substituted alkylene or arylene polyamine, 0.03
0.03 810
240 (A) 9.0 (B) 15.4 49 67 1.76 0.63 (A) 150 to 360 20 to 300 160 to 300 73 to 360 418 '26.4
(B) 120 '61.8 117 174 b) an antimony thiocarbamate or dithiocarbamate of the formula N - C - X - Sb wherein R is aliphatic or aromatic hydrocarbon radicals with 4 to 18 carbon atoms, X is oxygen or sulfur, at least one X being sulfur, and c) optionally an alkylated bisphenol of the formula OH OH wherein YS, O, Se or an S - S-, S - CH ₈ -, CH ₂ -S- CH ₈ -, CH (CH ₃ ) -, CH (C ₂ H ₅ ) -, C (CH ₃ V, C (C _a H ₅ ) ₂ -, (CH ₂ KS or NH group means contains.
2. Lubricating oil according to claim 1, characterized in that it contains a mixture in which antimony thiocarbamate and bisphenol are present in a weight ratio of 9: 1 to 1: 1. 709 710/533 12.67 © Bundesdruckerei Berlin