DE1285658B - Lubricating oils - Google Patents

Description

Cold sludge dispersants such as long chain alkyl methacrylate - η - vinyl - pyrrolidone copolymers and fatty methacrylate - diethylaminoethyl - methacrylate copolymers, are known. Compounds that have both high temperature detergent and cold sludge dispersing properties have not yet been proposed.

It is from U.S. Patents 2,947,740 and 2,969,324 and from British Patent Specification 867 800 known that phosphorus sulphurized hydrocarbons or their hydrolysis and neutralization products are useful lubricating oil additives. Although these compounds have a useful detergent action, they lack the ability to disperse the cold sludge.

The present invention now consists in a lubricating oil containing a neutralized phosphorus sulphurized one Polyisobutene or polybutene, which by reaction of an oil-soluble polyisobutenes or Polybutene with phosphorus pentasulphide has been obtained, as well as common lubricating oil additives with the mark, that it contains a phosphorus sulphurized polyisobutene or polybutene, which with an aliphatic or aromatic di- or polyamine or an amine of the general formula

R \ / R ⁴

have spergier- as well as high-temperature detergent effect.

As the acidic phosphorus-sulphurized polybutene, one is used which is composed of an oil-soluble polybutene Polybutene with a molecular weight of 750 to 5000, preferably from 900 to 2000, through Reaction with phosphorus pentasulfide has been obtained. The term "polybutene" includes polyisobutylene.

Particularly preferred is a polymer (polymer A) with a molecular weight of 2500 to 2600, which is obtained from a polyisobutylene fraction (molecular weight 1100) by reaction with P ₂ Ss (3.8 and 7.3%).

Di- or polyamines are those which contain either two or more primary amino groups or optionally the structure

R ¹

N - R ³ - N

_R5

/ CH ₂ CH ₂ ν
HN NR ⁶

N-R ³ -N

R ₂

HN

N - R ⁶ or

where R ¹ , R ² and R ^{4 are} H or -CH ₃ , R ^{3 is} an alkylene radical which can be substituted by alkyl or hydroxyalkyl radical or the group - (CH ₂ CH ₂ ^{NHXr -, R 5} - CH _{; !} or —CH ₂ CH ₂ OH or together with R ⁴ from the group

CH ₂ CH ₂

CH ₂ CH ₂

where R ¹ , R ² and R ^{4 are} hydrogen or CH ₃ , R ^{3 is} an alkylene radical which is optionally substituted by an alkyl or hydroxyalkyl radical or is the - (CH ₂ CH ₂ NH) _x CH ₂ CH ₂ group, R ^{5 is} CH ₃ or -CH ₂ CH ₂ OH or together with R ⁴ from the group

- CH ₂ CH /
consists, R ^ö H,

- CH ₃ - CH ₂ CH ₂ OH
or

- (CH ₂ CH ₂ NHXrCH ₂ CH ₂ NHo

CH ₂ CH ₂ NH ₂

CH ₂ CH ₂

consists, R ^e H,

- CH ₃ - CH ₂ CH ₂ OH - CH ₂ CH ₂ NH ₂

- (CH ₂ CH ₂ NH) ^ CH ₂ CHoNH ₂ and χ is an integer from 1 to 100, the compound not having any interfering polar groups, e.g. B. hydroxyl, sulfhydryl and carboxyl groups, may contain in the ß and positions to the primary amino group.

The organic di- or polyamine can also have the formula

"NH ₂ - (CH ₂ CH ₂ -NHXr-CH ₂ -CH ₂ -NH ₂

and χ represents an integer from 1 to 100 has been implemented.

US Pat. No. 2,688,612 already discloses similar compounds as high temperature detergents has been described. These are olefinic polymers that are phosphorus sulphurised and then hydrolyzed to remove inorganic phosphoric acids. The resulting Products are then brought into contact with alkaline earths and finally neutralized with formation of lubricant additives with high-temperature detergent effect.

In contrast, the present invention creates new products by using certain olefins for phosphorus sulphuration and also by using certain amines which neither have to be hydrolyzed nor brought into contact with alkaline earths and which have both cold sludge, in which χ is 1 to 100.

Preferred di- or polyamines are the polyethylene polyamines, like ethylenediamine etc.

Aromatic diamines such as p-phenylenediamine, o-phenylenediamine and benzidine are also suitable, cycloparaffinic diamines such as menthane diamine and simple aliphatic diamines such as hexamethylene-1,6-diamine.

Suitable amines are e.g. B.

N, N ₍ N ', N'-Tetramethyl-1,3-butanediamine, 2-aminoethylethanolamine,

3-dimethylaminopropylamine, 3-morpholinopropylamine,

2-aminoethylpiperazine,

2-hydroxyethylpiperazine,

9-morpholino-10-hydroxyoctadecylamine, 9-dimethylamino-10-hydroxyoctadecylamine.

The claimed lubricating oils are additive amounts of 0.1 to 10 percent by weight, preferably 1.0 to 5.0 percent by weight, added.

In addition, the claimed lubricating oils can also contain copper deactivators that lower the dropping point Agents, antioxidants, viscosity index improvers, etc.

The reaction of the acidic, phosphorus sulphurized polybutenes with the organic di- or polyamines are in the presence of a mineral ι ο lubricating oil or another diluent, z. B. with heating of the reactants carried out.

In general, the reactants are reacted in equimolecular proportions. The mole ratios but can also from 0.5 to 2 mol and preferably from 0.8 to 1.2 mol of di- or Polyamine per mole of phosphorus sulfurized polybutene can be varied.

Example!

288 g of phosphorus sulphurized polyisobutylene (polymer A) was dissolved in the same weight of light spindle oil at 70 ° C. 12 g of triethylenetetramine were stirred into the mixture at 70 ° C. and finally 1.44 g of benzotriazole as a copper deactivator added, the temperature being increased to 105.degree. The preparation was then filtered using filter gauze in a steam jacketed Buchner funnel filter. Further Di- and polyamine salts of polymer A are given in Table I.

The polymer A was treated as in Example 1 in Examples 2 to 13. After heating to 100 to 0.5 C, nitrogen was briefly vigorously blown in and filtered. Benzotriazole was not added here. The procedure for the remaining examples was to mix initially in the cold, then to heat the products to 150C to blow nitrogen for 2 hours at this temperature and then inject further at 95 ³ C air for 2 hours.

Polymer B

In a 700 ml short-necked flask equipped with a reflux condenser, stirrer, thermometer attachment, device for introducing solids and two nitrogen introduction pipes, 180 g of a commercially available polybutene were obtained (Molecular weight 110) weighed out.

The polybutene was heated to 220C with stirring and 27 g of phosphorus pentasulphide in the process of 20 minutes, a stream of nitrogen being passed through the oil during the process became. The product was then heated under nitrogen for a total of 8 hours stirred at 220.degree.

Polymer C

This was prepared in the same way as polymer B from 310 g of a polybutene (molecular weight 1900) and 27 g of P2S5. The P2S5 was added over 45 minutes at 220 ⁰ C and the reaction mixture stirred under nitrogen at this temperature for a further 10 hours.

Polymer D

74.5 g polybutene (molecular weight 900) were heated with 13.5 g P2S5 at 220X in a beaker, the total reaction time being 4½ hours.

% P

% S

Total acid number

Saponification value
(mg ■ KOH / g)

Polymerisa!

Typical
Numerical values

3.8
7.3
35

B. C. D. 2.4 3.8 4.8 6.1 4.7 6.4 41 26th 50 71 55 109

The corresponding amine salts of B, C and D were made in exactly the same way as the salts made from polymer A.

In all examples of amine salts, equimolecular amounts of acidic phosphorus sulfurized Polybutene and amine used, with the exception of Example 2 (4 mol of polymer A to 3 moles of triethylenetetramine).

Table I.

Di- and polyamine salts of polymers A, B, C and D

Amine Salts of Polymer A Example 2 Triethylenetetramine Example 3 Triethylenetetramine Example 4 Ethylenediamine Example 5 Diethylenetriamine Example 6 Tetraethylene pentamine Example 7 p-phenylenediamine Example 8 o-phenylenediamine Example 9 Menthane diamine Example 10 2-aminoethylethanolamine Example 11 Tetramethyl-1,3-butanediamine Example 12 Hexamethylene-1,3-diamine Example 13 Benzidine Example 14 3-dimethylaminopropylamine Example 15 3-morpholinopropylamine Example 16 2-aminoethylpiperazine Example 17 2-hydroxyethylpiperazine Example 18 9-morpholino-10-hydroxy octadecylamine Example 19 9-dimethylamino-10-hydroxy- octadecylamine Example 20 a polyamine (commercially available) Salts of Polymer B Example 21 Triethylenetetramine Example 22 Hexamethylene-1,6-diamine Salts of Polymer C Example 23 Triethylenetetramine Salts of Polymer D Example 24 Triethylenetetramine

Cold sludge dispersion test
Conditions:

using a standard H ^ -type Lauson machine under the following

Part A Part B

Part C.

Speed, rpm

Water drain, C

Fuel consumption, time (seconds) per 25 cm

Ignition timing, below the *
top dead center

oil temperature in the pan, C ....

Crankcase ventilation
Diff. inch. Water .

Duration in hours ...

700 51.5

235 ± 5

approximately 29.4 (unchecked)

1840
38

60 ± 2

25th
about 32.2

5
5

1840 99

60 ± 2

25th

82 (checked)

5 50

The total duration of the experiment was 100 hours, with Parts A and B, each optionally 5 hours long expired during the first 50 hours and Part C immediately thereafter for the remaining 50 hours. During the test, instead of 25 normal crankcase ventilation, the exhaust gases Introduced into the crankcase ventilation via a secondary line under slight pressure.

Substantial amounts of cold sludge were formed under these test conditions, with the 30th Machine cleanliness based on the weight of the sludge on the ram cover and in the oil pan and the appearance of the oil pan, tappet coating and forehead cover was determined, which were determined after a performance evaluation, in which 10.0 a completely clean coating and 0 a completely silted coating represent. The weight of the sludge in the oil pan was the most important criterion.

A and B are commercial detergents. X and Y are commercially available dispersants.

Table II Lauson machine trials

attempt

Ulgemiseh

Mineral oil A

Mineral oil A with 3.7 "0 metallic cleaning agent A. 0.9 ° u zinc dialkyldithiophosphate

Mineral oil A with 1.9 ° 0 metallic cleaning agent B. 0.7 "ο zinc dialkyldithiophosphate

Mineral oil A with 3.0 ° 0 dispersant X

Mineral oil A with 3.0 ° 0 dispersant Y

Mineral oil A with 1.6 ° 0 product from Example 3. 0.7 ° 0 zinc dialkyldithiophosphate

Repeat Experiment No. 34 using a different approach from example 3

*) Average number of three attempts.
**) Average number of two attempts.

Sioßelüber / ug Sehlammeeweight (gl

2.3 0.35

0.50 0.20 2.45

0.12 0.30 Leislungshew he! around

5.4

7.7

8.1
8.0
2.0

8.1

7.5

Stirmiberzug performance evaluation

5.7 8.1

7.9 8.3 5.0

8.3 9.1

TJ! tub

Sludge

weight

146 59

68 51 27

17 29

AT-4 cleaning test using a Petter AV-1 machine:

Duration of experiment 120 hours

Speed 1500 rpm

Braking power 5.0 HP

Performance evaluation

3.1

3.0 3.2 3.8

6.4

2.5

The machine was cooled with kerosene.

oil pan temperature 54.6 ± 1.8 ^C C

Coolant outlet temperature 85 ° C

Coolant inlet temperature 78.5 ± 1.3 ° C

Fuel O.4o / o sulfur

The AT-4 conditions are explained in "Institute of Petroleum Standards for Petroleum and its Products" as method IP 175/60 T.

Table III

36

Mineral A with

3.7% metallic

Detergent A,

0.9% zinc dialkyldithio

phosphate

Attempt no.

37 y

Lubricant preparation

38

Mineral oil A with

1.55% metallic

Detergent B,

0.75% zinc diaSkyl

dithiophosphate

Mineral oil A with 1.6% Example 2, 0.7% zinc dialkyldithiophosphate (Experiments were carried out with 3 different approaches from Example 3 in two different Engines carried out)

reviews
(Lack of 10 assuming)

1. Average Ring-groove-lacquer (A) ...

2. Average Felder paint (B)

3. Edge area paint (C)

A + B + C

4. Bottom paint

7.2 7.7

0.7 15.6

5.6

4.1

5.2

0.08
9.4

2.8

6.75 3.9 6.4 4.1 0.80 0.45 13.95 8.5 6.4 5.3

7.1 5.6

1.15 13.9

6.0

Oxidation stability test at high temperatures according to the Institute of Petroleum Test IP J. 76/60 T with Petter-W-I machines:

Duration of experiment 36 hours

Speed 1500 ± 15 rpm

Braking power, about 3.3 hp

oil pan temperature 138 ^C C

Coolant outlet temperature 150 ± 0.9 ° C

Coolant inlet temperature 148.5 ± 0.9 ° C

Fuel ΡΕ / IP or petrol '

39 Table IV Attempt no.
41 42 • 43 Oil preparation Detergent A
3.6
0.9
10.0
8.4
8.9
27.3
5
10.7 40 Example 2
1.6
0.7
9.8
7.0
6.8
23.6
12th
17.6 Example 3
1.6
0.7
9.3
7.4
7.3
24.0
7th
2.5 Example 4
1.6 -
0.7
10.0
8.5
8.3
26.8
8th
3.7 Detergent
Dispersant,%
Zinc dialkyldithio
phosphate,%
Piston edge rating (A)
Field evaluation (B)
Groove rating (C)
A + B + C
Storage weight loss, mg ..
Increase in viscosity of the oil,
cSt at 38 ° C Detergent B
1.6
0.7
9.7
8.5
7.6
25.8
8th
4.5

The mineral oil A was a solvent-refined mineral oil with a viscosity of approximately 160 Redwood I seconds at 60 ^° C.

Claims (1)

Claim: Lubricating oil containing a neutralized, phosphorus sulphurized polyisobutene or polybutene, which by reaction of an oil-soluble polyisobutene or polybutenes with phosphorus sulfide has been obtained as well as customary lubricating oil additives, characterized in that that it contains a phosphorus sulphurized polyisobutene or polybutene, which with an aliphatic 809 64Ä / 1574 or aromatic di- or polyamine or an amine of the general formula R ¹ ^ R ⁴ R ₂ / Ν —R ³ —N HN NR ⁶ IO ^X CH ₂ CH ₂ ^/ where R ¹ , R ² and R ^{4 are} hydrogen or CH ₃ , R ^{3 is} an alkylene radical which is optionally substituted by an alkyl or hydroxyalkyl radical or the - (CH ₂ CH ₂ NH) ^ CH ₂ CH ₂ - Group means R ⁵ = CH ₃ or - CH ₂ CH ₂ OH or together with R ⁴ from the group -CH ₂ CH ₂ O - CH ₂ CH ₂ / consists, R ⁶ = H, -CH ₃ -CH ₂ CH ₂ OH -CH ₂ CH ₂ NH ₂ or - (CH ₂ CH ₂ NH) ^ CH ₂ Ch ₂ NH ₂ and λ: represents an integer from 1 to 100, has been implemented.