DE2511905A1 - NEW BASIC LUBRICANTS FOR MULTI-RANGE OILS - Google Patents

Description

The present invention "relates to new base lubricants for multigrade oils.

The production of multigrade oils from mineral or synthetic hydrocarbon oils generally requires the addition of relatively large amounts of additives to improve their viscosity index, which in general have the disadvantage of inadequate thermal and mechanical stability when the oils are extreme Are exposed to conditions related to temperature and load. Therefore, to reduce the viscosity index improver Additives have already been suggested that

509839/0936

Hydrocarbon oils> in a mixture with different

to use synthetic oils, for example with esters of diacids, esters of polyols, esters of polyalkylene glycols as well as esters of ethers of the condensation of an alkylene oxide with compounds with one or more hydroxyl groups.

It has now been found that certain compositions of the type of complex esters mixed with mineral or synthetic Hydrocarbon oils can advantageously be used as base lubricant components for multigrade oils can.

The present invention relates to new basic lubricants for multigrade oils, essentially consisting of homogeneous mixtures of

(a) in an amount from 50 to 99% by weight of at least one lubricious mineral or synthetic hydrocarbon oil,

(b) an amount of 1 to 50 wt. # of at least one composition of a complex ester and

(c) an amount from 0 to 60% by weight of at least one light weight Esters,

which have a means of improving the viscosity index in one Amount has been added that is necessary to achieve the viscous imetric characteristics that are desired SAE category, these basic lubricants are characterized in that said composition is a complex ester between at least one polycarboxylic acid, namely a possibly hydrogenated dimeric or trimeric acid of unsaturated fatty acids, at least one dihydroxyl compound, namely a polyalkylene glycol or a diol, and at least a monofunctional compound consisting of at least one monocarboxylic acid or at least one compound with a Hydroxyl group, namely a monoalcohol (or monophenol) or a monoalcohol (or monophenol) oxyalkylene compound, is formed, provided that at least one of the compounds having one and two hydroxyl groups is a compound with oxyalkylene groups.

50983 97 0936

The compositions of complex esters according to the invention can on the one hand (a) from the esterification of a dimeric acid of an unsaturated fatty acid with at least one compound with two hydroxyl groups, which consists of at least one polyallylene glycol or at least one common diol ^ xaid laii at least one compound with a hydroxyl group, which consists of at least one monoalcohol (or monophenol) oxyalkylene compound and / or from at least one common monoalcohol (or monophenol), with the proviso that at least one of the compounds with one and two hydroxyl compounds contains oxyalkylene groups, the various reaction components are used in amounts which practically correspond to 2 moles of dimeric acid to 1 mole of compound with two hydroxyl groups and 2 moles of compound with one hydroxyl group.

You can also (b) from the esterification of such a dimer acid and at least one monocarboxylic acid with at least one Compound with two hydroxyl groups, which consists of at least one polyalkylene glycol (preferably a polypropylene glycol), emerge, the various reaction components are used in this Pail in amounts that are practically 1 mol dimeric acid and 2 moles of monocarboxylic acid correspond to 2 moles of polyalkylene glycol.

The compositions of complex esters according to the invention can also (c) from the esterification of a trimeric acid of an unsaturated Fatty acid with - as indicated above under (a) for the dimer acid - at least one compound with two hydroxyl groups (Polyalkylene glycol or common diol) and at least one compound having a hydroxyl group (monoalcohol or monophenol-oxyalkylene compound and / or common monoalcohol or monophenol), with the condition that at least one of compounds with one and two hydroxyl groups contains oxyalkylene groups, the various reaction components are used in amounts that this time practically 2 moles of trimeric acid to 1 mole of compound with two hydroxyl groups and 4 moles

'80983970936

Compound with a hydroxyl group correspond.

You can also (d) from the esterification, such a trimer Acid and - as stated above under (b) for the dimer acid - at least one monocarboxylic acid with at least a polyalkylene glycol (preferably a polypropylene glycol), the reaction components being used in quantities that this time practically 1 mole of trimeric acid and 3 moles Monocarboxylic acid correspond to 3 moles of polyalkylene glycol.

The compositions of complex esters according to the invention can furthermore (e) consist of the esterification of mixtures consisting of different amounts of dimeric and trimeric acid with a compound having two hydroxyl groups and a compound having one hydroxyl group, as indicated above under (a) or (c) , result, the various reaction components are used in .solchen Ifengen that for 2 moles (dimeric -ι- trimeric) acid practically 1 mole of compound with two hydroxyl groups and as many moles of compound with one hydroxyl group as necessary for the esterification of the remaining carbon functions are _o

You can finally (f) from the esterification of mixtures, which consist to different parts of dimer + trimer acid, and moiiocarboxylic acids with a polyalkylene glycol, as indicated under (b) and (d), originate, the reaction components being used in such amounts that practically there are practically 2 moles of polyalkylene glycol and as many moles of monocarboxylic acid as for the esterification per mole of (dimer + trimer) acid the remaining hydroxyl functions are required.

According to the invention you can also use (g) Esterkompo sit ions, as they are mentioned above under (a), but in which one practically 3 moles of dimeric acid to 2 moles of compound with two hydroxyl groups and 2 moles of compound with one hydroxyl group begins. In the above description, these compositions fall under the term “compositions of complex esters”.

B09839 / 0936

Mixtures of at least one can also be used according to the invention two of the ester compositions described above under (a) to (g).

Of the ester compositions defined above under (a), (c), (e) and (g) especially those in which the compound having two hydroxyl groups are essentially considered consists of a polyalkylene glycol (preferably a polypropylene glycol). In this case you are connected to a Hydroxyl group advantageously from a monoalcohol or monophenol-oxyalkylene compound (preferably a monoalcohol or monophenol-oxypropylene compound) or from a mixture consisting of a monoalcohol or monophenol-oxyalkylene compound (preferably a monoalcohol or monophenol oxypropylene compound) and an ordinary monoalcohol or monophenol consists.

Of the ester compositions defined above under (g) it is also possible to use advantageously those in which the compound with two hydroxyl groups consists essentially of an ordinary diol, while the compound with one hydroxyl group essentially from a monoalcohol or monophenol-oxyalkylene compound (preferably a monoalcohol or Monophenol-oxypropylene compound).

In order to enable a more detailed description of the compositions of complex esters used according to the invention, the following are given below details the various compounds from which they can be formed.

The dimers and trimer used in the present invention Acids originate in particular from dimerization or trimerization unsaturated fatty acids containing 14 to 22 carbon atoms; this dimerization or trimerization can be followed by a hydrogenation connect. The dimeric acids therefore generally contain 28 to 44 and the trimeric acids 42 to 66 carbon atoms .

6098 3-9 / 0936

Examples of dimeric or trimeric acids are the those from the dimerization or trimerization of the following unsaturated Fatty acids originate;

~ Tetradecenoic acids (like myristoleic acid),

- -hexadecenoic acids (such as palmitoleic acid),

- octadecenoic acids (such as oleic acid),

- Octadecadienoic acids (like linoleic acid) and octadecatrienoic acids (like linolenic acid), Eicosenoic acids,

Docosenoic acids (such as erucic acid or brassidic acid), as well as natural or synthetic mixtures of several of these acids, such as:

- the soy fatty acids, which include about 25 $ octadecenoic acid,

45 $ octadecadienoic acid and 7 $ octadecatrienoic acid contain,

- the fatty acids of linseed oil, including about 20 $ octadecenoic acid, Contain 15 $ octadecadienoic acid and 50 $ octadecatrienoic acid,

- the fatty acids of whale oil, which include about 5 $ tetradecenoic acid, 15 $ hexadecenoic acid, 35 $ octadecenoic acid and 1 $ contain octadecadienoic acid,

- the fatty acids of rub oil, including about 18 $ octadecenoic acid, 19 $ octadecadienoic acid, 8 $ octadecatrienoic acid,

Contains 6 $ eicosenoic acid and 42 $ docosenoic acid.

The di- and tricarboxylic acids derived from the di- or trimerization of hydrocarboxylic acids may also be mentioned, such as ricinoleic acid.

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The oligomerization of the unsaturated fatty acids of the type mentioned above generally results in complex mixtures which mainly trimers, dimers and the unreacted monomers Contain acids. From these mixtures came? man, ζ, B. by means of fractional distillation, the dimers and uie xrimers Separate acids or mixtures of dimeric and trimeric acids.

The dimeric and trimeric acids preferred according to the invention are those which result from the dimerization or trimerization of unsaturated Fatty acids with 18 carbon atoms originate (e.g. oleic, linoleic or linolenic acid); they become pure or natural or synthetic mixtures are used which contain a larger proportion of the acids mentioned.

The polyalkylene glycols which come into consideration in the present invention correspond to the general formula

H 4 - R ₁ \ OH

in which R ^ is an alkylene-1,2 radical, preferably a propylene-1,2 radical, and the number n, which indicates the average degree of polycondensation of the polyalkylene glycol, has a value from 2 to 50 and mostly from 2 to 30. That is, the polypropylene glycols particularly used in the present invention have a average molecular weight from about 130 to 3000 and mostly from about 130 to 1800.

The diols used in the present invention correspond to the general formula HO - R '- OH, where R' is divalent Hydrocarbon radical and in particular a divalent saturated aliphatic radical, e.g. 2 to 20 carbon contains atoms. Examples of these diols include the following: ethylene glycol, 1,3-propanediol, 1,4-butanediol,

5098 3 9/0936

Keopentyl glycol, pentanediol-1,5, hexanediol-1,6, trimethyl-2,2,4, 1,3-pentanediol, trimethyl-2,2,4- and -2,4,4-1IeXaIIdIoI-IJe, Dodeeandiol-1.10. You could too. Use moles that are not the correspond to the above general formula and the remainder of which can contain an ester function, such as neopentyl glycol hydroxypivalate.

The monoalcohols and monophenols used according to the invention correspond in particular to the general formula R ₂ - OH, where R _{2 is} a monovalent hydrocarbon radical which is an aliphatic radical with 1 "to 25 carbon atoms, an alicyclic radical with 3" to 25 carbon atoms or an aromatic radical with 6 can be up to 25 carbon atoms.

The following are examples of aliphatic monoalcohols called: methanol, ethanol, n-butanol, ethyl-2-hexanol, isononanol, Isodecanol, dodeeanol, isotridecanol or isopentadecanol,

as examples of alicyclic monoalcohols: Cyclopropanole Cyclobutanol, Cyclohexanol or methyl cyclohexanol, and as examples of monophenols: The phenol itself and the phenols, the nucleus of which is substituted by one or more alkyl groups is like the dodecylphenol, the nonylphenol or the Heptylphenol.

The monoalcohol and monophenol-oxyalkylene compounds used in the present invention correspond to the general formula R ₂ - 0 -f R ₁ - 0 ^ _n , H, where R ₁ and R ₂ are defined as above and n ^{1 is} a number from 1 to 50 is; the group R ₁ is in particular a propylene-1,2-G group, and the number n 'preferably has a value from 1 to 30.

The monoalcohol and monophenol oxypropylene compounds so defined generally have an average molecular weight of from about 90 to 2800, and especially from about 90 to 2100, each according to the type of monoalcohol or monophenol and degree of polycondensation of propylene oxide. As examples of this mono alcohol or

509839/0936

Monophenol-oxypropylene compounds may be mentioned which from the condensation of propylene oxide with the aliphatic or alicyclic monoalcohols or with those mentioned above Monophenols originate.

The monocarboxylic acids used in the present invention correspond to the general formula IU COOH, where R 'is a monovalent one Hydrocarbon radical and especially a monovalent one is an aliphatic radical having 1 to 25 carbon atoms.

The following are examples of monocarboxylic acids: heptanoic acid, ethyl-2-hexanoic acid, pelargonic acid, isonanoic acid, isodecanoic acid, undecenoic acid, dodecanoic acid, the isostearic acids, the fractions resulting from the fractional distillation of the fatty acids, as well as the natural or synthetic mixtures of several saturated or unsaturated fatty acids.

The compositions of complex esters used according to the invention can be prepared by means of any conventional esterification process v / earth, in which the carbon and hydroxyl compounds defined above are used in appropriate amounts, of course Instead of the carboxylic acids themselves, their halides or lower alkyl esters can be used.

After any purification, for example by means of distillation and / or passage over activated fuller's earth or aluminum oxide, the complex esters according to the invention are in the form of a viscous liquid, the density of which is generally close to the unity. Their viscosity at 98.9 ⁰ C can se]
can be, for example, 30 to 200 cSt.

their viscosity at 98.9 ° C can vary widely; she

They generally have a high viscosity index, e.g., about 150 to about 250.

509839/0936

The base lubricants according to the invention can consist of binary mixtures of compositions of complex esters as defined above and mineral oils. In this case, in particular, the mineral oils refined by means of solvents, the mineral oils refined with acid and the hydro-refined mineral oils, ie
Have 100 to 600 SSÜ.

nated mineral oils, which have a viscosity at 37.8 C of about

The two constituents can be contained in these basic lubricants in different proportions: e.g. 1 to 40% by weight, - preferably 5 to 20 wt. $, At least one composition of complex esters according to the invention to 60 to 99 wt. 5 ^, preferably 80 to 95 wt. ^, Of at least one mineral oil. In particular, be these amounts are used so that the amount of viscosity additive that is optionally added to the mixture to the To achieve viscosity characteristics that correspond to the desired SAE category is as low as possible.

About the viscometric characteristics of the base lubricants made from mixtures of complex esters according to the invention and mineral oils exist, to compensate and, if necessary, to improve the miscibility of the constituents with one another, the invention provides before adding one or more light esters to the mixtures mentioned, such as:

- esters of dicarboxylic acids and monoalcohols, such as isodecyl adipate, the isotridecyl adipate ^ the trimethylhexyl azelate, the Ethyl hexyl sebacate, octyl and decyl trimethyl adipate;

- esters of monocarboxylic acids and polyols, such as trimethylolpropane pelargonate, neopentyl glycol pelargonate, trimethylolpropane heptanoate laurate;

- Or esters of mono- or dicarboxylic acids and alcohol-polyoxyalkylene compounds with a weak degree of condensation, such as the laurates or the dodecanedioates of butanol-polyoxypropylene compounds, the viscosity of which can be, for example, between 5 and 30 cSt at 37.8 ° C;

509839/0936

- or esters of monocarboxylic acids and polyoxyalkylene glycols of low molecular weight, such as polyoxypropylene glycol dilaurate with a molecular weight of 300,

The proportion of these light esters in the basic sizing agents can be e.g. 10 to 60% by weight, preferably 10 to 40% by weight. In In this case the proportion of mineral oil is, for example, 50 to 80 wt and the proportion of complex ester, for example 1 to 40% by weight.

The basic lubricants according to the invention can also be made from mixtures complex esters exist, as described above for the synthetic hydrocarbon oils. In this case the synthetic hydrocarbon oil can consist of, for example:

- a polymer obtained by polymerizing olefins having 2 to 20 carbon atoms, such as the polyisobutenes, the have an average molecular weight from 200 to 2000 and preferably from 300 to 500,

- and one optionally partially or fully hydrogenated

mono- or polyalkylated aromatic compound, v / ie dem Didodecylbenzene and didodecylcyclohexane.

The ingredients are in these mixtures, depending on their type and characteristics of the synthetic hydrocarbon oil used, in Amounts of, for example, 1 to 40 weight percent of the complex ester of the invention per 60 to 99 weight percent of synthetic hydrocarbon oil contain.

The base lubricant can also contain varying amounts of light esters, as mentioned above.

In order to obtain the final lubricating oil products and especially multigrade oils, the basic lubricants described above are added usual amounts of conventional additives in, 'in particular

- Phenol, amine, or antioxidants

509839/0936

organometallic compound such as zinc alkyldithiophosphate;

- Dispersing additives such as derivatives of succinimides, methacrylic copolymers with nitrogen function;

- and organometallic detergents such as sulfonates, phenate sulfides, Salicylates, phosphonates.

As stated above, there is one of the advantages of the basic lubricants according to the invention in that they the formulation of multigrade oils with little or even do not allow any conventional viscosity additive to be added.

Another important advantage is that the presence of the complex esters of the present invention in the base lubricant, this one is strong over that of the hydrocarbon oils give improved wear resistance so that, if necessary, one can rely on the use of specific wear resistance additives can dispense, which can have certain significant disadvantages: The effectiveness of these additives can in the course of Time lag because they generally have insufficient hydrolysis resistance and relatively poor heat resistance sum part can be used up.

It is therefore important to have basic lubricants such as those according to the invention Represent basic lubricants, which themselves have good wear resistance properties, so that Satisfactory lubrication is guaranteed throughout the entire service life.

In addition to their use in the production of motor oils, the lubricating compositions according to the invention can be used on other similar ones Areas are used, especially in the production of hydraulic fluids or oils for the processing of metals (e.g. cutting and shaping).

5098 3 9/0936

The following examples serve to explain the invention, which, however, is in no way limited by these examples. Examples 12 and 21 are listed for comparison.

Manufacture A

Under normal esterification conditions, esterification of a dimer acid gives unsaturated fatty acids with 18 carbon atoms with a mixture of polypropylene glycol and alcohol-polyoxypropylene compounds in amounts of 2 moles of dimeric acid to 1 mole of polypropylene glycol and 2 moles of alcohol-polyoxypropylene compound produced a complex ester.

The dimer acid used is a commercially available dimer acid with molecular weight 565, saponification number 191-198 and a purity of $ 95 (EMPOL 1040 from UNILEVER-EMERY).

The polypropylene glycol used has a molecular weight of 400 and contains about 7 propylene oxide elements per molecule.

The alcohol-polyoxypropylene compound comes from the condensation of propylene oxide with a mixture of saturated aliphatic monoalcohols having 13 to 15 carbon atoms. It has a viscosity at 37.8 ⁰ G of about 100 cSt, and contains about 20 propylene oxide elements per molecule.

The characteristics of the complex ester obtained are as follows:

Viscosity at 37.8 ° C "701 cSt

¹¹ at 98.9 ° C 84 cSt VI _E 222

Pour point -30 ⁰ C

Manufacturing B

Under conventional esterification conditions one has by esterifying a polypropylene glycol by means of a mixture of a dimer acid of unsaturated fatty acids with 18 carbon atoms and lauric acid in amounts of 2 moles of polypropylene glycol to 1 mole dimeric acid and 2 moles of lauric acid produce a complex ester

509839/0936

posed.

The dimer acid and polypropylene glycol used are those same as in production A.

The characteristics of the complex ester obtained are as follows:

viscosity ⁷¹ E. at 98.9 ° 0 308 cSt π Pour point at 39 c St. Manufactures 188 and E - 36 ⁰ C C. D

Under normal "esterification conditions" one has by esterification a trimeric acid of unsaturated fatty acids with 18 carbon atoms by means of mixtures of polypropylene glycols and alcohol-polyoxypropylene compounds in amounts of 2 moles of trimeric acid to 1 mole of polypropylene glycol and 4 moles of alcohol-polyoxypropylene compounds three complex esters produced.

The trimeric acid used is a commercially available trimer Acid of molecular weight 850, saponification number 192-200 and purity of $ 95 (EICPOL 1040 from UNILEVER-EMERI).

The polypropylene glycols used have a molecular weight of 134 or 400 or 1200. They contain about 2 or 7 or 20 Propylene oxide elements per molecule. The alcohol-polyoxypropylene compound comes from the condensation of propylene oxide with a Mixture of saturated aliphatic monoalcohols with 13 to Carbon atoms. It has a viscosity at 37.8 ° C of about 100 cSt and contains about 20 propylene oxide elements per molecule.

The characteristics of the complex esters obtained are as follows Table I listed.

509839/0936

- 15 Table I.

Her j complex ester based on viscosities

stelig. ^ based on

(cSt)

at 37.8% at 98.9 ° C j

, ο, i ^VI E

! Flow point ( ⁰ G)

Polypropylene glycol 134

Polypropylene glycol 400

Polypropylene glycol 1200

: 930; 8.94 1160

112.4

\ 110.6

142.5

j

231 ι
j 231

! 243

-27 -24 -24

Manufactures F, G and H

Under conventional esterification conditions, esterification of polypropylene glycols by means of mixtures of a trimeric Acid of unsaturated fatty acids with 18 carbon atoms and lauric acid in amounts of 3 moles of polypropylene glycol to 1 mole of trimer Acid and 3 moles of lauric acid produced three complex esters,

The trimeric acid and polypropylene glycols that have been used are the same as in Preparations C through E.

Me characteristics of the complex esters obtained are shown below Table II listed.

Table II

Her- complex ester on stelig, based on

I "PolypropyYes ^ glykoL 134 G. "400

H »1200

Viscosities
_ (cSt)

Ibei 37.8 ⁰ C at 89.9 ⁰ C

VI

525 604 736

54.5
69.5
93.6

; 178 200 227

Pour point ( ⁰ C)

-24 -27 -27

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25119Ü5

Examples 1 to 11

From a mineral oil 280 neutral, the aim was to produce multigrade oils belonging to the category SAE 20 ¥ 40 belong.

The mineral oil and each of the complex esters A through H were mixed in the amounts shown in Table III below and a light JEster in the also indicated Quantities added. In addition, each mixture has the specified amount of viscosity additive (commercially available polymethacrylate! 2 Antioxidant and 5 wt. ^ Detergent added.

The characteristics of the oils obtained are given in Table III below.

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Table III

oil
No.

CO! OO CO!

CO ■ CO

1
2
3
4th
5
6th
7th
8th
9
10

. Basic ingredients. .Mineral oil ..jcompl. Ester

Io j Art

280 N j 57
280 NJ 60

280 N.

280 N.
280 N.
280 N.
280 N.
280 N.

CO

280 N j 70

70 70 70 70 56

280 N j 70

280 N j 70

A A B C D E F G G H G

13 12 15 15 15 15 15 15 13 15 13

Art

30th

JTMP-C ₉ j

j DA. 01.10-C ₁₂ yrs

j Λ j A j A j A j A YES

j A jDA, 01..10 € _12!

20 15 15 15 15 15 31 15 17

14.34

Viscosity at

!easier. Ester Ibitäts-p8,9 ° C -17.8 ⁰ C

(O In ₀₁₁ , rf addition j ^ _{ς + Λ} ( _Poise )

39

38.5

39

57

• 55.5
55.5
49.5
49
40

'51, 5
40

j IA, 2

j 12.8

j 15.2

j 15.1

15.7

ί 13.18

j 13.58

! 14.26

j Π.4

! 14.30 y

■ ·

j L

j 159

158

ι.

j 150 j "-12

J 146

j 147

j 150

j 142

j 145 j -18

j 157 j -15

j 147 j -13

j 157! -13

-16 -14 -15 -14

(2)

A 10 β isodecyl adipate

TMP-Cg s trimethylol propane pelargonate

DA.01.10-C.2 = polyoxypropylene butanol laurate with approx

Mineral oil 280 neutral = 50/50 mixture of 200 DJ and 5 propylene oxide elements

350 N

-33 -33

-36

-33 -36 -30 -33 -36 -36

-30 ι \>

4 »

It can be seen from Table III above that by that the multigrade oils 1 to 11 contain complex esters is possible, very small amounts of viscosity additives to use.

Several of these basic substances for multigrade oils were tested on machines to check the friction resistance, namely on the four-ball machine, the Amsler wear machine and the I ¹ ZG machine. For the sake of comparison, a 200 SSU mineral oil was also tested which had been given the same viscometric characteristics by means of a viscosity additive (Table IV).

- With the help of the tests on the four-ball machine, the load capacity, expressed by the load-wear index (ASTM D 2783-71), and the wear diameter can be determined under load (test duration: 1 hour).

Compared to the reference formula are the load-wear indices and the results regarding the wear and tear under load is significantly improved.

The abrasion tests (chrome-plated piston ring, cast-iron cylinder) were carried out on an Amsler disk machine under gradual loading of 10 to 10 daK at a sliding speed of 4 m / sec. carried out, wherein the oil had a temperature of 100 ^0C . Some formulas had excellent abrasion resistance properties compared to commercially available mineral oils and significantly lower coefficients of friction.

- An improvement from 2 to 3 has been made on the PZG machine "Degrees of damage" determined against the mineral oil.

The oils according to the invention therefore show against the base oil on the machines to check the frictional strength and the Wear significantly improved behavior.

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Table IV

Testing the oils on machines for verification the friction resistance

"T

oil
No.

Debit

Lock, index Kgf

^ ier.-Ball-Mas.ciiine

Load J sweat | Mittl. ^ FerH;] ^ ißi £ D ± nies3sr in before the | strengi_ jnui_Xi hour.) .-

! seize up

Jgf UsL

1 ! 34.7 20 W 40!

2! 34.5

20 W 40!

9! 24.8 20 W 40!

i i

'11! 29.9!

20 W 40! ■!

t t

12 *! 22.4 !

20 W 40! !

80

63

50

63

50

200

200

200

30 K

50 K A.brieb- Reibg. -lastgjkoeff

; .- jPemperat.
Γ. at begin

»J tv ι

nend, l! est-

0.75! 0.86

0.67! 0.73 ι

j ι

0.68! 0.76 ι

! 200! 0.65! 0.70

! I 160! 0.72! 1.68 '! 0.043! 236

! 0.042!

! 0.087!

ι ι

! ι

J L

begtor just

> 200 ι 0.036! > 240 J 9

ι ι i

! 0.045! 238

ι j

j ι

10

228

!

! 0.340 j

! j

! 0.186

! 0.330! ! !

! 0.149 ! ! !

0.208

⁺ 'Oil 12: 200 Neutral + Antioxidant Detergent Additives + 6.5 $ viscosity additive (reference oil)

VO

■ - 20 -

Manufacture J

Under normal esterification conditions one has a complex one Esters made by adding 2 moles of a dimeric acid unsaturated Fatty acids with 18 carbon atoms with 1 mole of polypropylene glycol and then with a mixture consisting of 1 mole the alcohol-polyoxypropylene "compound described under Preparation A and 1 mole of a common monoalcohol, namely a mixture of branched, saturated aliphatic monoalcohols with 9 to 11 carbon atoms (registered trademark ACROPOL 91).

The dimer acid and polypropylene glycol used are the same as in preparation A.

The characteristics of the complex ester obtained are as follows; Viscosity at 37.8 ⁰ C

at 98.9 ⁰ C

^VI E

FliessOunkt

691 c St. 80 cSt 207 -27 ⁰ C

Manufacturing K

An ester composition is obtained under the usual esterification conditions prepared by adding 3 moles of a dimeric acid of unsaturated fatty acids with 18 carbon atoms with 2 moles Neopentyl glycol and then with 2 moles that described in preparation A. Has implemented monoalcohol polyoxypropylene compound.

The dimer acid used is the same as in preparation A, The features of the ester composition obtained are as follows:

Viscosity at 37.8 ⁰ C "at 98.9 ° C

Pour point

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1398 cSt 148 cSt 227 -21 ⁰ C

Examples 13-17

By adding the ester compositions J and K to various mineral and synthetic hydrocarbon oils one wanted to produce multigrade oils of the category SAE 20V / 40. The mineral oils are oils of the type 200, 280 and 300 neutral ^ una the synthetic Hydrocarbon oil (referred to as "alkylate") is an alkylbenzene in which the alkyl substituent. mainly from at least one dodecyl radical and the

- a viscosity at 37.8 ⁰ C of 27.8 cSt,

- a viscosity at 98.9 ° C of 4.6 cSt

- and a Vl-g of 80 having.

The hydrocarbon oils and the ester compositions J and K were mixed in the amounts given in Table V below. Some of these mixtures became a light ester in the specified Amounts added, and the specified amount of polymethacrylate, 2% by weight of antioxidant and 5% by weight of detergent has also been added.

The characteristics of the oils obtained are also given in Table V.

Examples 18-20

From a mineral oil consisting of a mixture of different One wanted to divide a 100 neutral oil and a 150 neutral oil by adding the ester compositions A, J and K to multigrade oils of the class SAE 10 ¥ 30.

The mineral oil wur.de with each of the ester compositions in the in the amounts given in Table V below, without the addition of a light ester. The specified ones were added Amount of polymethacrylate, 2% by weight of antioxidant and 5% by weight of detergent.

The characteristics of the oils obtained are also given in Table V.

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From Table Y it can be seen that by having oils 13 to 20 contain a complex ester, the multigrade oils only contain very small amounts of additives to improve the viscosity index (Polymethacrylate) needed to be added.

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Table V

oil Basic consignment & ._ Weight * complex Weight # I light ester 15th Poly Viscosity be (Poise) No. Hydro oil Art j type ^ 'wt. $ - meth 98.9 ⁰ C
(cSt) Art 70 15th 15th acrylate 49.5 (2) 91 J 9 TMAOD - 15.0 85.0 13th 280 N. 75 J 10 - - 2 13.2 46.5 14th 300 N 90 .K 10 TMAOD - - 13.15 62.5 15th 280 N. 85 K 15th - - 2 15.4 '38, 0 16 200 N 92 K 8th - - 3 14.1 24 17th Alkylate 83 A. 17th - 3 10.2 24.0 18th 140 N 86
J 14th 2 9.83 23.5 19th 120 N K ■ - 9.87 20th 120 N

(D

TMAOD: octyl and decyl trimethyl adipate

Mineral oil 280 Neutral «50/50 mixture of 200 N and 350 H

"300" a 3O / 7O mixture of 200 Ή and 350 N

¹¹ 140 "= 20/80 mixture of 100 N and 150 Ή

»120» = 50/50 mixture of 100 N and 150 N

Some of these multi-disc oils have been put on machines for review the friction resistance (4-ball and FZG machine) tested. For comparison, an oil 150 neutral was also tested, to which the addition of polymethacrylate gave similar viscose properties became.

The results are given in Table VI:

"On the" 4-ball ⁿ "machine, load-wear indices and wear results were obtained which are considerably better than those obtained with the reference oil.

- On the FZG machine, an improvement of 2 "degrees of damage" is achieved compared to your Basugsöl.

509839/0936

Table VI

σι ο co

co. co ^ * O co co CD

feiscKleiß
3elastg, - 4-ball machine Sweat avg. Wear and tear
load gauge in mm (1 hour) 30 K 50 K 70 K PZG Specific
Ibnutzg. oil no .: index
Kgf Debit
before the Kgf 0.77 0.89 1.70 Scha
dens-. ig / ch.h 29.2 Pestfres
sen Kgf 200 0.74 0.84 '2.05 grade ι ι
0.175 18th
10 W 30 28.4 63 200 0.71 0.76 2.00 9 0.192 19th
10 W 30 29.7 50 . 200 0.81 1.67 2.13 9 0.122 20th
10 W 30 19.2 63 160 9 0.175 21 *
10 W 30 40 7th

oil 21 (reference oil)

150 neutral + viscosity additive (3 (xew. #)
+ Antioxidant (2 wt. #)
+ Detergent (5 wt. ^)

ro

Claims (32)

- 26 claims ) Lubricating composition for use as a basic lubricant for multi-grade oil, essentially consisting of the homogeneous mixture (a) an amount of 50 to 99 wt. ^ of at least one lubricious mineral or synthetic hydrocarbon oil, (b) an amount of 1 to 50% by weight of at least one composition complex ester and (c) an amount from 0 to 60% by weight of at least one light weight Esters, which one means of improving the viscosity index in one Amount has been added which is necessary to see the viscometry corresponding to the desired SAE category To achieve characteristics, characterized in that said composition of complex esters between at least one Polycarboxylic acid, namely an optionally hydrogenated dimeric or trimeric acid of unsaturated fatty acids, at least a compound having two hydroxyl groups, namely a polyalkylene glycol or one mole, and at least one mono-functional compound has been formed from at least one monocarboxylic acid or at least one compound with a hydroxyl group, namely a monoalcohol or monophenol or a monoalcohol or monophenol-oxyalkylene compound, exists, provided that at least one of the compounds having one and two hydroxyl groups is a compound having oxyalkylene groups. 2) Composition according to claim 1, characterized in ₅ that said composition of complex esters of d.er esterification of a dimer acid of at least one unsaturated fatty acid, "which contains 14 to 22 carbon atoms, with at least einsr compound having two hydroxyl groups, a polyalkylene glycol and swar of the general formula Hf ~ 0 - .R ₁ -I - = - OH ₅ , where R _{1 is} an alkylene-1,2 radical and η is a number from 2 to 50, or one mole of the general formula HO - R | - OE, where R ₁ ^{1 is} a divalent hydrocarbon radical, and with 509839/0 9 36 at least one compound with a hydroxyl group, namely a monoalcohol or monophenol of the general formula R - OH, where Rp is an aliphatic alicyclic or aromatic monovalent radical, or a monoalcohol or monophenol-oxyalkylene compound of the general formula R_ - 0 - f - R. - 0 -) -, H, where R. and R ₂ v; ie are defined above and n ^{1 is} a number from 1 to 50, the reaction components are used in amounts that practically 2 moles of dimeric acid to 1 mole Compound with two hydroxyl groups and 2 moles of compound with one hydroxyl group. 3) Composition according to claim 2, characterized in that the reaction components are used in amounts that are practically 3 moles of dimeric acid correspond to 2 moles of compound with two hydroxyl groups and 2 moles of compound with one hydroxyl group. 4) Composition according to one of claims 2 and 3, characterized in that that the compound with two hydroxyl groups consists essentially of at least one polypropylene glycol and the compound having a hydroxyl group contains at least one monoalcohol-oxypropylene compound. 5) Composition according to claim 3, characterized in that the compound with two hydroxyl groups consists essentially of at least an ordinary diol and the compound having a hydroxyl group consists essentially of at least one monoalcohol-oxypropylene compound consists. 6) Composition according to claim 1, characterized in that said composition of complex esters from the esterification of a dimer acid of at least one unsaturated fatty acid containing up to 22 carbon atoms, and at least one monocarboxylic acid of the general formula RACOOH, where R ' _{2 is} a monovalent hydrocarbon radical , with at least one compound with two hydroxyl groups, namely a polyalkylene glycol of the general formula H - {- 0 - R ₁ -) - OH, where R ₁ 509839/0936 ⁿ is an alkylene-1,2 radical and η is a number from 2 "to 50, the reaction components being used in amounts that are practically 1 mole of dimeric acid and 2 moles of monocarboxylic acid correspond to 2 moles of compound with two hydroxyl groups. 7) Composition according to claim 6, characterized in that the compound having two hydroxyl groups consists essentially of at least a polypropylene glycol. 8) Composition according to one of claims 2 to 7, characterized in that that the dimeric acid originates from the dimerization of at least one unsaturated fatty acid which has 18 carbon atoms contains. 9) Composition according to claim 1, characterized in that said composition of complex esters from the esterification of a trimeric acid of at least one unsaturated fatty acid containing 14 to 22 carbon atoms with at least one compound with two hydroxyl groups, namely a polyalkylene glycol of the general formula H - f - O - R ^ - ^ - OH, where R. is an alkylene-1,2 radical and η is a number from 2 to 50, or a diol of the general formula HO - R ¹ * - OH, where R '.. is a divalent hydrocarbon radical, and with at least one compound with a hydroxyl group, namely a monoalcohol or monophenol of the general formula R ₂ - OH, where R _{2 is} an aliphatic, alicyclic or aromatic monovalent radical, or a monoalcohol or monophenol -Oxyalkylene compound of the general formula R _? - 0 - (- R ₁ - 0 -} -, H, where R ₁ and R _{2 are} as defined above and n ^{f is} a number from 1 to 50, the reaction components being used in amounts that are practical 2 moles of trimeric acid correspond to 1 mole of compound with two hydroxyl groups and 4 moles of compound with one hydroxyl group. 10) Composition according to claim 9, characterized in that the Compound with two hydroxyl groups consists essentially of at least one polypropylene glycol and the compound with a hydroxyl group at least one monoalcohol 509839/0936 contains oxypropylene compound. 11) Composition according to. Claim 1, characterized in that said composition of complex esters from the esterification of a trimeric acid of at least one unsaturated fatty acid containing 14 Ms 22 carbon atoms and at least one monocarboxylic acid of the general formula R'p COOH, where R * ^ is a monovalent carbon / is hydrogen radical, with at least one compound with two hydroxyl groups, namely a polyalkylene glycol of the general formula H — f- 0 — Ri -) - _n OH, where R .. is an alkylene-1,2 radical and η is a number is from 2 to 50, the reaction components being used in amounts which correspond to practically 1 mole of trimeric acid and 3 moles of monocarboxylic acid per 3 moles of compound having two hydroxyl groups. 12) Composition according to claim 11, characterized in that the compound with two hydroxyl groups consists essentially of at least a polypropylene glycol. 13) Composition according to one of claims 9 to 12, characterized in that that the trimeric acid originates from the trimerization of at least one unsaturated fatty acid containing 18 carbon contains atoms. 14) Composition according to one of claims 4, 7, 10 and 12, characterized in that the polypropylene glycol has 2 to 30 oxypropylene groups contains. 15) Composition according to one of claims 4, 5 and 10, characterized in that that the monoalcohol-oxypropylene compound contains 1 to 30 oxypropylene groups. 16) Composition according to claim 4, characterized in that the dimer acid from the dimerization of unsaturated fatty acids with 18 carbon atoms, the compound with two hydroxyl groups is a polypropylene glycol with a molecular weight from about 130 to 1,800 and the compound with a 509839/093 6 Hydroxyl group a monohydroxyl polyether of the condensation of propylene-1,2-oxide with an aliphatic monoalcohol with 13 "to 15 carbon atoms, which contains about 20 propylene-1,2-oxide elements contains per molecule. 17) Composition according to claim 16, characterized in that said compound having a hydroxyl group is also an aliphatic monoalcohol with 9 "to 11 carbon atoms contains. 18) Composition according to claim 5 »characterized in that the dimer acid comes from the dimerization of unsaturated fatty acids with 18 carbon atoms, the compound with two hydroxyl groups the neopentyl glycol and the compound with a Hydroxyl group a monohydroxyl polyether of the condensation of propylene-1,2-oxide with an aliphatic monoalcohol with 13 to 15 carbon atoms, of the about 20 propylene oxide elements contains per molecule. 19) Composition according to claim 7 »characterized in that the dimer acid originates from the dimerization of unsaturated fatty acids with 18 carbon atoms, the compound with two hydroxyl groups is a polypropylene glycol with the molecular weight of about 130 to 1,800 and the monocarboxylic acid which is lauric acid. 20) Composition according to claim 10, characterized in that the trimeric acid from the trimerization of unsaturated fatty acids with 18 carbon atoms, the compound with two hydroxyl groups is a polypropylene glycol of molecular weight is from about · 130 to 1,800 and the compound with a Hy ~ droxylgruppe a monohydroxypolyether of the condensation of propylene-1,2-oxide with an aliphatic monoalcohol with 13 to 15 carbon atoms, of the about 20 propylene-1,2-oxide elements contains per molecule. 50983 9/0936 21) Composition according to claim 12, characterized in that the trimeric acid from the trimerization of unsaturated fatty acids with 18 carbon atoms, the compound with z * -; ei Hydroxyl groups a polypropylene glycol of the ko "! Ecular weight s is from about 130 "to 1,800 and the monocarboxylic acid is lauric acid is. 22) Composition according to one of claims 1 "to 21, characterized in that the hydrocarbon oil is a solvent- or acid-refined mineral oil or a hydro-refined mineral oil, which have a viscosity at 37.8 ⁰ C of about 100 to 600 SSU. 23) Composition according to one of claims 1 to 21, characterized in that that the hydrocarbon oil is one of the olefin polymers or one of the mono- or polyalkylated aromatic Is compounds which are optionally at least partially hydrogenated. 24) Composition according to one of claims 1 to 23, characterized in that that said homogeneous mixture is essentially 60 "to 99% by weight of hydrocarbon oil and 1 to 40% by weight Contains composition of complex esters. 25) Composition according to claim 24, characterized in that the said homogeneous mixture essentially 80 to 95 wt. $ hydrocarbon oil and 5 to 20 wt. 5 ^ composition more complex Contains ester. 26) Composition according to one of claims 1 to 23, characterized in that that said light ester is a simple ester of dicarboxylic acids and monoalcohols, a simple one Esters of monocarboxylic acids and polyols, a simple ester of mono- or dicarboxylic acids and monoalcohol-polyoxyalkylene compounds with a low degree of condensation or a> -; * Esters of monocarboxylic acids and polyoxyalkylene glycols is of low molecular weight. 509839/0936 27) Composition according to claim. 26, characterized in that said homogeneous mixture contains 10 to 60% by weight of light ester contains. 28) Composition according to claim 27, characterized in that said homogeneous mixture 10 to 40 wt. $ Light ester contains. 29) Composition according to one of claims 27 and 28, characterized in that said homogeneous mixture 50 to 80 wt. $ Hydrocarbon oil and 1 to 40 wt. $ Composition
contains complex ester. 30) multigrade oil, characterized in that it contains a larger amount of a lubricating composition according to one of claims 1 to 29, including the appropriate amount of additive to improve the viscosity index, which is required to achieve the viscometric characteristics corresponding to the desired SAE category, as well as a smaller one
Contains an amount of an antioxidant and a smaller amount of a detergent. 31) Multigrade oil according to claim 30, which belongs to the SAE category 20 ¥ 40. 32) Multigrade oil according to claim 30, which belongs to the SAE category 10 ¥ 30. 509839/0936