DEN0007118MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: April 30, 1953. Advertised on December 8, 1955

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 23c GROUP 1 oi TS 7118 IYcI23c

Forrest Jay Watson, Emeryville, Calif. (V. St. A.)

has been named as the inventor

N. V. De Bataafsche Petroleum Maatschappij, The Hague

Representative: Dr. K. Schwarzhans, patent attorney, Munich 38

Lubricants based on esters of phosphoric acids,

of silicas, carboxylic acids and compounds

with linear polymer chains

The priority of registration in the V. St. v. Claimed America May 2, 1952

The invention particularly relates to high quality composite lubricants, in particular which for use as hydraulic fluids or as lubricants for internal combustion engines are suitable and which are resistant to degradation by oxidative or thermal influences and have exceptional corrosion properties.

According to the invention, the aim set is achieved by using the as a lubricant base Esters of phosphoric acids, silicic acids, carboxylic acids or the long-chain ones suitable for this purpose polymeric compounds minor amounts of an epoxy compound and a metal salt of a Incorporated condensation product of an aldehyde and a phenol or thiophenol. The two

509 598/123

N7118IVc / 23c

Additives are supposed to be essentially related to the lubricant base be mixable.

The use of metal salts of the condensation products of aldehydes and phenols or thiophenols!) As a lubricant additive was known per se. Also wui'd ^'one already proposed polymerized lipoxyverbindungen itself as a lubricant base to use.

Through the combined use of the two

to components, however, becomes a synergistic effect achieved, which could not be foreseen due to the effect of one of these additives. Mixtures with the most favorable properties are obtained by adding each of the additives in an amount

if, from 0.1 to ό weight spro / .ent, particularly useful 0.5 to.:, 5 G 'wiclitspro / .ent, ber.'hn -t on the Total mix, used.

Epoxy compounds are those organic compounds the ι oxygen atom in bond to

so '2 carbon atoms! · contain which in turn already connected in other ways. As Kpoxyverbindungen, which in the invention Mixtures are effective, for example, the following can be listed:

Pine oxide, butadiene oxide, 1,2-epoxy ~ 3-aminopro-Itan, Glyeidylpheiiyläther.Epichlorhydrin, 2,3-Epoxy-. '| -Chlorl) iitan.

Polyepoxides, d. H. Compounds containing more than one epoxy group can also be used will. J) these can be monomeric compounds that have more than one epoxy group, or also polynierized compounds. The latter compounds can be of any one the monomeric monocpoxvde, and some of their epoxy groups can be hydrated or implemented in some other way. You can have molecules with slightly different molecular weights contain.

This type of connection can be used as an addition

4 »also play the glycidyl polyethers of the polyvalent ones, e.g. B. dihydric phenols are expected, the by reacting a polyhydric phenol with a large excess, ζ. Β. an excess from.) to 8 mol, of a halogen-containing epoxide in

■ t. ^r > alkaline medium.

The other additive is a metal salt of a condensation product of an aldehyde and a phenol or thiophenol. Suitable phenols and thiophenols, of which the condensate derive ionsprodukle, are for example dibutylthiophenol, Anylphenol, octylphenol, octylthiophenol, p-isooctylphenol, alkylaminoplienol, alkylaminonaphthol and the like

To form the conditioning products with the

: ">;> the above compounds can be aliphatic e, aromatic or other cyclic aldehydes can be used. Examples of suitable aldehydes are formaldehyde, acetaldehyde, crotonaldehyde, bulyraldehyde, benzaldehyde and fiirfuraldehyd.

Γι »The Kondeiisalioiisprodukte can after known Process can be prepared using an acidic or a basic catalyst. As salts of the condensation products mentioned come alkali, Alkaline earth or heavy metal salts into consideration, for example the Ca, Ba, Sr, Na, K, Li, Al and Zn salts.

Phosphorus-containing esters, which are used as a lubricant base useful within the present compositions include those normally liquid aliphatic Esters of acids of phosphorus, for example hydrocarbon off phosphonsäiiredialkylester, in particular dialkyl alkylphosphonate, alkyl dialkylphosphinate, 2 compounds containing phosphorus atoms, such as bis (dialkylphosphonic) alkanes, and the corresponding ethers of the aforementioned diphosphorus compounds.

The phosphorus «! Esters, which are in particular highly suitable for the combination of additives according to the present invention usually have a total of at least one carbon atoms and preferably about 20 to 32 carbon atoms Molecule, for example phosphoric acid triliexyl ester, phosphoric acid tri (isooctyl) ester, phenylpliosplionic acid dihexyl ester and diheptylphosphinic elexyl ester.

The compounds containing 2 phosphorus atoms include, in particular, aliphatic ^; Hydrocarbons, by two phosphorus-containing groups in the form of phosphate, phosphonate, pliosphinate or phosphine oxide groups are substituted. Beziig- yo borrowed the hydrocarbons which the latter Carrying kind of substituents, it can be noticed that these are not esters in the real sense of the word are. However, they are analogous to the other compounds and, like these, can be used in the compounds according to the invention Mixtures can be used as a lubricant base.

It is of course not necessary to have connections to be used with a symmetrical structure. For example, the various substituents be different within a given compound, both in terms of Content of carbon atoms as well as with regard to the spatial configuration. The branched Structures are preferred because they generally have a better effect on lubricant properties exercise, especially at low temperatures. Are unsaturated hydrocarbon radicals especially desirable when attached directly to a phosphorus atom, since their Presence improves the corrosion properties of the lubricant.

The class of compounds containing 2 phosphorus atoms have favorable properties with respect to of use as hydraulic fluids. In general, their viscosities are between 10 and 25 cSt at about room temperature. The compounds in which 2 carbon atoms are direct are connected to one or both phosphorus atoms, in particular the diesters of alkanediols and iao Dialkylphosphinic acids, have much higher viscosities, which makes them more than synthetic lubricating oils are particularly suitable.

Another suitable lubricant base are the esters of organic carboxylic acids, especially those complete esters of aliphatic dicarboxylic acids,

501) 508/12)

N 7118 IVc / 23c

for example adipic acid di- (2-methylheptyl) ester, ■ Dioctyl phthalate, di (2-ethylhexyl) sebacate, Allyl caprylate, as well as their homologues, analogues and derivatives. Tri-esters such as B. trioctyl aconitate, are also well suited.

Silicic acid esters also behave very favorably versus the incorporation of the combined additives of the present invention. The silicic acid esters include alkyl, aryl, aralkyl and alkylaryl esters of silicon-containing acids, such as ortho-, metha- and polysilicic acid esters. Typical examples from this group are silicic acid tetra (2-ethylhexyl) ester, Tetraphenyl silicates, tetracresyl silicates and tetradecyl silicates.

Particularly suitable esters are also made by esterifying acids of silicon and phosphorus or obtained from polycarboxylic acids with sulfur-containing alcohols. The esters thus obtained have excellent properties at high pressures, and they speak to the combined according to the invention Additives particularly well.

Compounds with polymeric linear chains, the exist as oxyalkylene units.

The typical formula of such polymers is

where η is an integer and R is an organic radical. In these polymers, all or some of the oxygen atoms can be replaced by sulfur atoms. Polymers of this group can be prepared by polymerization or copolymerization of alkylene oxides, glycols and sulfur-containing analogues thereof.

In addition to the additives combined according to the invention, smaller amounts of other additives can be added to the Lubricant mixtures are incorporated in order to improve certain properties of the same. Examples for such additives are the polymerized methacrylic acid esters (which come under the trade name »Acryloid« are marketed), 2,6-di-tert-butyl-4-methylphenol, phenyla-naphthylamine and bis (p-dimethylaminophenyl) methane.

To get the synergetic effect created by using the two additives together in is achieved with the mixtures according to the invention, two types of tests were used.

According to experiment A, carefully cleaned and polished metal sheets made of a magnesium alloy, an aluminum alloy and copper, steel and cadmium measuring 2.54 x 2.54 cm and 0.08 cm thick are placed in 100 ml of the oil mixture to be tested for 168 hours heated to 121 ⁰ , with about 51 air being passed through per hour. The metal strips are put together in the order magnesium, aluminum, copper, steel according to a square and the cadmium strips are arranged on the diagonal. This entire arrangement is suspended in the test mixture, and after the end of the test, the individual metal strips are washed and dried, and the loss of corrosion is determined by weighing. Experiment B differs only in that the metal strips are heated to .121 ° for 71 hours, while 11 air per hour is passed through 20 ml of the test mixture. Test A is described in detail in Military Specification MIL-0-5606. The following Tables I and II show the test results obtained with various lubricant mixtures, in addition to the corrosive effect of the same on the various metals, the acid number at the end of the test and the percentage increase in viscosity caused by oxidation under the given test conditions.

It can be seen that mixtures which do not contain any additives within the meaning of the present invention cause severe signs of corrosion in most cases, especially with copper, in many cases, however, also with cadmium. In addition, the tables show that an addition of either the Metal salt of the condensation product or the epoxy compound alone the corrosion of one or several of the metals tested are not sufficiently prevented. One by the numbers in the tables The additional effect shown consists in the reduction of the acid number and in the percentage increase the viscosity, which by oxidation under the conditions of the two above-mentioned test methods caused.

Further mixtures according to the invention are listed below:

lubricant

Caproic acid-1,3,5-heptane triol ester

Trioctyl aconitate

Copolymer of ethylene glycol and trimethylene glycol

Butadiene monoxide

i, 2-epoxy-3-aminobutane

Pinene oxide

i, 2-epoxy-5-ethoxypentane ....

Mg salt of a formaldehyde-hexylphenol condensation
product

Ba salt of an acetaldehyde-dibutylphenol condensation product

Zn salt of a crotonaldehyde-2-ethylhexylphenol condensation product

example
24 I 25 26

27

98

509 598/123

Claims (2)

N7118IVc / 23c Table I. lubricant example j ₇ 14 15 Dinonyl-ß, ß'-thiodipropionate ι, 5-IVntanediol-bis-dil) utyl phosphate l'lexol 20i ^s ) J'lexol. '.).) ^{: 1} ) Silicic acid - (^ - ätliylhexyl) -eslcr I'henylphosiihonsänredi hex ylester J1 ex ylphosphonic acid hexyl ester Glycidyl phyl ether Oc'tylfnrmol ¹ ) ' 2, o-ditrrt.-butyl-.i-methylphenol Acryloid 111 "8125 Attempt Λ Cu CD Al Säiire / ahl "/ ,, Viscosity increase iing · '<■' 37.7 " (Percentage by weight of the individual components of the total mixture) 98.0 1.0 1.0 9.91 ο 1.16 0.91 5 ° 97.5 98.0 1.0 100.0 98.0 1.0
1.0 92.0 ι, o
7, ° 91.0 1.0 1.0 1.0 6.0 91.2 2.0 1.0 5.8 97.5 (Weight change in mg / cm ^{2 of} the metal surface) I. 72 23 , 4 0.15 4th , 00 O , 16 13th , 5 0.05 25th , 57 - - 0 0 0 O , ° 4 0 , 46 0.06 4th M. - - 0 0 0 O > ° 5 IO , 3 1.09 32 , 2 5 , 0 27 , 0 21.0 Μ , 5 1.98 0 6.56 0.12 7, o 0.03 53.3 0.09 82.8 0 50.12 0 - O, O2 +0.03 0 0.05 0 ο, 16 0.04 - O, O2 + 0.10 0 12.2 0 7.28 o, i6 5, o O, O2 0.24 0.02 0.02 0 0.24 0.08 - 0.04 - (- 0.02 0 39.6 0.01 7.24 0.14 - - 10.25 0.44 35,000 4, ° 70.0 5, o ii, 5 8.0 0.02 0.02 0.02 0.02 1.62 ') Ca salt of the condensation product of formaldehyde and octylphenol.
^a ) Scbaciiisauic-di-fi-ethylhexyl-ester.
^{; t} ) adipic acid di-isnoctyl ester. Table II lubricant 16 example
19 20 l'henylphosphonic acid diisooctyl ester I, 5-1 'cntanediol-bis-dibut ν! Phosphate ClycHlylphenylathcr OcI ylfoniiol Attempt B Cu M « Fc CD Λ1 Samczah] "/" Viscosity creamy at 37.7 ° (Percentage by weight of the individual components of the total mixture) 100.0 20.24 27.44 ο 5.12 0.04 49.4 I i6, o 98.0 98.0 1.0
1.0 98.0
1.0
1.0 98.0
2.0 (Weight change in mg / cm ^{s of} the metal surface) 16.56 23.3 0.36 118.0 0.08 O
O
O
O 1.49
9, o 0.04 2.72 0.52 3.44 O 0.28 0.16 0.48 0.04 0.04 0.08 0 O 0.28 0.08 °> ° 4 O 0.08 O O, O / | !, 24 3.52 0.65 i, 38 7.0 100 3.0 1.0 P AT! ■: N TA NSPR O C II E: I. Lubricants based on esters of phosphoric acid!), Silicas, carboxylic acids or compounds with polymeric linear chains, characterized by a content of a Kpoxyverbindungen and a metal salt known as a lubricant additive of a condensation product of an aldehyde and a phenol or a Thiophenol in amounts of preferably 0.1 to (1 percent by weight and in particular from 0.5 to 2.5 percent by weight of each component, based on the total mixture. 2. Lubricant according to claim 1, characterized in that that the epoxy compound is a glycidyl alkyl ether or a glycidyl aryl ether, in particular contains a Glycidylphcnyläther. References: U.S. Patents Nos. 2,562,144, 2,573,568, 580 274. O 509 598/123 11.55