DE1237721B - lubricant - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

169 /

ClOm

A28

German: 23 c-1/01

Number:
File number:
Registration date:
Display day:

1237 721
S 76807IV c / 23 c
November 23, 1961
March 30, 1967

It is known that polypolar copolymers, the basic amino nitrogen groups or hydrocarbon groups and / or contain oil-soluble carboxylic acid groups as substituents, for improvement the detergency, the viscosity index and the pour point of lubricating oils are suitable. Such lubricating oils, however, need to be improved their properties also have phosphorus and / or Sulfur compounds are added.

Also known are lubricants which act as dispersants and copolymers to reduce wear contain, which by reaction of a polymerizable, basic, heterocyclic nitrogen compound, like vinyl pyridine, with another polymerizable compound, but none Groups with heterocyclic! Containing nitrogen, such as acrylic acid esters, can be obtained. For improvement These lubricants also need other additives to prevent wear and tear. ζ. Β. Metal salts of organic sulfonic acids.

It has now been found that lubricants have an improved cleaning effect and a reduced A tendency to sludge formation can be obtained if a mineral lubricating oil is used from 0.1 to 10 percent by weight of one or more copolymers added on the main hydrocarbon chain polar and optionally non-polar substitute lubricants

Applicant:

Shell International Research

Maatschappij N.V., The Hague

Representative:

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

Named as inventor:
Harry Francis Richards, Concord, Calif .;
Stephen Aven Herbert Jun., Weston ·, Conn .;
Robert James Moore, Orinda, Calif. (V. St. A.)

Claimed priority:
V. St. v. America November 25, 1960
(71403)

tuents bound in any or even arrangement, and are characterized by that they have the structural formula

CCC C

! I.

ι ~ ⁽

I.
R.

(a)

C - =

ι ι

R ¹

OH (b) -CC -

(C)

where R = an alkyl radical with 10 to 20 carbon atoms, R ¹ an alkylene radical with 5 to 7 carbon atoms, Y an alkyl radical with 12 to 20 carbon atoms or an ester, amide, amine or phosphate group, m and m, an integer, but at least 2, and η 0 or an integer and the ratio of m to / M ₁ between 10: 1 and 1:10 and of m + M ₁ to η between 10: 1 and 5: 1 and the molecular weight is between 1,000 and 1,000,000.

These copolymers are produced by copolymerizing an unsaturated compound

50 (monomer a), which contains an ester group - COOR, where R is a C ₁₀ -C ₂₀ -alkyl radical, another unsaturated compound (monomer b) which contains a COOR '- OH group in which R ^{1 is} a C ₅ -C ₇ alkylene radical, and optionally an unsaturated compound (monomer c) which contains a C ₁₂ -C ₂₀ alkyl radical or an ester, amide, amine or phosphate group.

Acrylic and alkacrylic acid esters of aliphatic alcohols with at least 8 carbon atoms are used as monomers (a), preferably with 10 to 20 carbon

709 547/369

atoms, such as decyl acrylate, lauryl acrylate, stearyl molecular weight of 175,000. The mixed polymer

Acrylate, eicosanyl acrylate, docosanyl acrylate, decylsate showed excellent cleaning properties.

methacrylate, lauryl methacrylate, methyl methacrylate,

Steary methacrylate and mixtures of these compounds - Example 4

gen, used. 5

The monomers (b) used are preferably ru-Hy- To a benzene solution containing 0.2% &, a'-azodiiso-

containing hydroxy esters of acrylic or alkacrylic acids and butyronitrile, were 2 moles of stearyl methacrylate,

Dihydroxyalkanes, which are straight-chain or branched 1 mole of 2-methyl-5-vinylpyridine and 1 mole of "-hydroxy-

Can be chain, preferably "," - dihydroxymyl methacrylate added. The mixture was

alkanes, such as χ, ω- Amylenglykol - (1,5-pentanediol), heated io 24 hours on 80 ⁰ C. At the end of the reaction *

Λ, ω-hexylene glycol, <x, ra-heptylene glycol, neopentyl time was an oil-soluble copolymer with a

glycol, used. Such esters include ro-hydroxy molecular weight obtained from 100,000, which is excellent

amyl acrylate, ω-hydroxyamyl methacrylate, ω -hy- had cleaning properties,
hydroxyhexyl acrylate, o-hydroxyhexyl methacrylate, cu-hy-

droxyheptyl acrylate, ω - hydroxyheptyl methacrylate, 15 B eis ρ ie 1 5
1,3-dimethyl-3-hydroxybutyl methacrylate and mixtures of these compounds. To a benzene solution containing 0.2% x.n'-azodiiso-

As monomers (c) Polyenkohlenwasser- butyronitril were contained, were 2 moles of stearyl methacrylate,

substances, such as Λ-unsaturated, long-chained hydrocarbons, 1 mole of bis-chloroethylvinylphosphonate and 1 mole

fabrics, e.g. B. decene-1, hexadecene-1, octadecene-1, 20 "-Hydroxyamyl methacrylate added. The mixture

5,5,7,7-Tetramethyldecen-l and 4,4,6,6-tetramethyl was heated for 24 hours at 80 C ^c. At the end of

hepten-1; unsaturated esters, e.g. B. vinyl decanoate, reaction time was an oil-soluble copolymer

Vinyl laureate and vinyl stearate; unsaturated ether, obtained with a molecular weight of 150,000, which

z. B. vinyl dodecyl ethers; Allyl esters or ethers, as shown to have excellent cleaning properties.

Allyl stearate; unsaturated amides, e.g. B. N-Laurylmeth- 25 If desired, the claimed

acrylamide and N-stearyl methacrylamide; Vinylpyridines, lubricants and other common additives, e.g. agents

z. B. 4-vinyl pyridine; Vinyl pyrrolidone; Vinylphospho- to improve the resistance to oxidation and

nates and allyl phosphates, e.g. B. Trimethallylphosphbat to avoid eating in amounts of 0.01 to

and bis-chloroethyl vinyl phosphonate are used. 2%, preferably 0.1% / ₀ to 1% by weight,

The polymerization can be given in the presence of an im 30.

essential inert solvent and in the presence of the copolymers are the lubricants

unit of an oxygen-supplying catalyst in an amount of 0.01 to 10 ° / ₀ and in particular of

Temperature in the range from 50 to 150 ⁰ C, preferably 0.1 to 10 ° / ₀ added. They are used for improvement

wise between 60 and 90 ⁰ C, are carried out. of transformer oils, turbine oils, mineral

The following examples explain the production of lubricating oils and technical oils. Appropriate

of the copolymers, but for this purpose such lubricating oils have a viscosity of SAE 5W

the invention claims no protection. to SAE 140. They are preferably derived from

paraffinic, naphthenic or asphaltic

Example 1 crude oils; for example, sophisticated ones are suitable for this

40 oils with a high viscosity index, such as mineral

To a benzene solution, which 0.2 ° / ₀ λ ,, - ji'-Azo- lische oils with a viscosity at 37.8 ⁰ C from 100 to

containing diisobutyronitrile became 2 moles of stearyl meth-250 SUS.

acrylate and 1 mole of fj-hydroxyamyl methacrylate to- A typical mineral lubricating oil (X) of these

set. The mixture was heated to 8O ⁰ C for 24 hours and had the following properties:

heated. At the end of the reaction time, an oil 45

"äiäf copolymer with a molecular weight of specific weight, ⁰ APl,

155,000 won, which is excellent 15 6/15 6 ⁰ C 32

properties showed. '

Flash point, ⁰ C 187.8

Example 2 50 Viscosity Index 93

To a benzene solution which has 0.2% / ₀ Å, * '- azodiiso viscosity, SUS at 37.8 "C 103

butyronitrile, 1.1 mol of stearyl methacrylate, 1.9 mol of lauryl methacrylate and 1 mol of ω-Hy- The following, non-ash-forming mixtures were added hydroxyamyl methacrylate. The mixture was 55 are typical examples of the invention:
Heated for 24 hours 8O ⁰ C. At the end of the reaction time, an oil-soluble copolymer with a mixture A weight percent molecular weight of 400,000 was obtained, which was excellent * ..,,. ^ 1 ™ · · 1 1 <*
Showed cleaning properties. Copolymer according to example 1 ... 2
^{6 ö s 6} _6o Mineral lubricating oil (X) rest

^Bei P ^{iel 3} GemischB

To a benzene solution containing 0.2% *, a'-azodiiso copolymer according to Example 2 ... 2

butyronitrile contained 2 moles of stearyl methacrylate mineral lubricating oil (X) balance

and 1 mole of 1,3-dimethyl-III-hydroxyamyl methacrylate 65. , _r

was added and the mixture was left on oemiscn C for 24 hours

8O ⁰ C heated. At the end of the reaction time, a copolymer according to Example 3 ... 2

oil-soluble copolymer obtained, which is a mineral lubricating oil (X) remainder

5 6

Mixture D. Weight percent EX-3, described in CRC Progress Report No. 3

Copolymer according to Example 4 ... 2 from 1/6/1957, compiled.

Mineral lubricating oil (X) remainder The term "active group" in the head of column 2

_,. , “The table refers to mixtures of

Mixture b _{5 experiment} j _{and 2} , which teaches the invention

Copolymer according to Example 5 ... 2 correspond, only to the type of substituents B im

Mineral lubricating oil (X) remainder of the copolymer, which is the structure

Mixture F

Copolymer according to example 1 ... 3 ~ ^COOR '- ^0H ( ^R ' = C ₅ - C ₇ alkylene)

4,4'-methylene-bis- (2,6-di-tert-butyl- ¹⁰ ,...

phenol) 1. The copolymers in mixtures A

Mineral lubricating oil '.'. '.'. '.'. '.'. '.'. '. Remainder ^{and B} differ with regard to the rest

polar substituents - COOK, since mixed poly-

Mixture G merisat in mixture A the remainder R the group - C ₁₈ H ₃₇

Copolymer according to Example 1 ... 2 15 and that of mixture B the groups

4,4'-methylene-bis- (2,6-di-tert-butyl- - C ₁₈ H ₃₇ and - C ₁₂ H ₂₅ means.

phenol) 0.5 The ratio multiplied by 100 is used as the VT value

Tricresyl phosphate 0.8 nis the relative increase in viscosity at 100 ⁰ C for

Mineral lubricating oil (X) denotes the remainder of the relative viscosity increase at 38 ^{° C.}

20 The mixture according to the invention according to Experiment No. 2

In the table, the results of the Chevrolet are in this regard much more favorable than the known

V-8 sludge test according to the modified test mixture according to experiment No. 4.

composition

Substituent B of the copolymer

Lacquer formation
on the
Pistons

a)

Total paint

Total sludge

c)

Final evaluation

d)

Oil ring

constipation

% Increase in viscosity at

37.8 ° C

VT value

1. Mixture A
Mixture B

2. Mineral oil (X) +2 _^0/0 copolymer of stearyl methacrylate and monomethacrylate hexylene glycol (molecular weight 143000)

3. Mineral oil (X) + 2% copolymer of stearyl methacrylate and hydroxyethyl methacrylate (Molecular weight 230,000)

4. Mineral oil (X) +2 ° / ₀ copolymer of N-vinylpyrrolidone and lauryl methacrylate (molecular weight 500,000)

5. Mineral oil (X) +2 ° / ₀ mixed polymer of lauryl methacrylate, stearyl methacrylate, 2-methyl-5-vinylpyridm (molecular weight 500,000)

O - C ₅ - OH O - C ₅ - OH C

O-C-C-COH C C

- O —C,

OH

CH ₂ - c;

CH ₂ -CH /

N-CH

H ₃ CC / ) C-

CH-OT

a) 10, perfect.

b) 50, perfect.

45.1
40.8
40.0

79.1
72.7
60

41.6

40.1

63.6

70.2

39.5

61.0

94.8 86.2 77.6

13th

13 13 50

81.5

84.0

16

23

25th

27

77.6

79

23

c) 100, perfect.

d) 100, perfect.

Lubricants according to the present invention are particularly for use at high temperatures and at high speeds, such as. B. in aircraft engines, automobile engines, tractors, as well as suitable for technical systems.

Claims (1)

Claim: A lubricant consisting of a mineral lubricating oil and 0.01 to 10 percent by weight of one or more copolymers with to the Main hydrocarbon chain bound polar and optionally non-polar substituents, characterized in that there are copolymers of the structural formula -C-C - C ι R (a) where R = an alkyl radical with 10 to 20 carbon atoms, R ¹ an alkylene radical with 5 to 7 carbon atoms, Y an alkyl radical with 12 to 20 carbon atoms or an ester, amide, amine or phosphate group, m and W _{1 is} an integer, but at least 2 and η 0 or an integer and the ratio of C = 0 R ¹ OH (C) to η is between 10: 1 and 5: 1 and the molecular weight is between 1,000 and 1,000,000. m 7Άΐη _Λ between 10: 1 and 1:10 and from m - \ - tri 1 053 699. Considered publications:
German Patent No. 960 756;
German Auslegeschrifts No. 1 003 896, 1 003 897, 709 547/369 3.67 ® Bundesdruckerei Berlin