DE1806401B - Power transmission fluid - Google Patents

Description

at least one branched paruflin, whose recurring catches up to at least 33% of the structure

H
C.

R,

IO

where R _{1 is} a WusscrstolTatom or a methyl radical and R ₂ . is an isopropyl or isobutyl resl;

J) a perhydrogenated polymer, copolymer or polymer of ' ⁵

1. styrene,

2. u-methylstyrene,

3. / i-methylstyrene or

4. a mono- or dimethylringsubsliluierten derivative of styrenes 1, 2 or 3;

e) a substituted C ₁₂ to C ₃₀ DeCaHn, which contains at least one of the radicals C _{1 to} C ₅ alkyl, C ₅ to Q cycloalkyl, C “to Qo alkylcyclohexyl and alkylcyclopentyl as a subsidiary ;

a highly refined naphthenic oil, which contains less than 1% gel-forming aromatic hydrocarbons;

g) a C ₁₃ - to C ₄₀ -naphthcn with the Perhydroterphenyi- or Perhydrofluorenrest as basic structure;

h) at least one C ₁₂ to C ₄₀ adamantane compound which does not contain any elements other than carbon, hydrogen, fluorine and oxygen and in which, in the presence of oxygen, it is in the form of an ether or ester compound; or off

i) a mixture of at least one of the constituents a), d), e), 0, g), h) with 0.1 to 20 parts by weight of at least one synthetic liquid polymer, copolymer or terpolymer of a C ₃ to C ₈ olefin .

The invention will be described in detail in connection with a power transmission system, the one Pull drive and as a lubricant for this includes a medium which is predominantly in the lubricating oil area boiling hydrocarbon base with a kinematic viscosity at 98.89 ° C in the range of 1.5 to 200, contains OcSt. This hydrocarbon base contains at least one hydrocarbon, of a perhydrogenated polymer, copolymer or terpolymer of styrene, u-methylstyrene, / i-methylstyrene or alkyl, cycloalkyl and alkylcyclohexyl derivatives this corresponds to perhydrogenated polymers, copolymers or terpolymers.

In the following description, the designation of liquids which have such a perhydrated Containing dimers or codimers of these styrenes, the term "hydimer" is used.

Fluorine substitution products of the hydrocarbons mentioned, in which one or all of the hydrogen atoms of the hydrocarbon has been replaced by fluorine, are also suitable as transmission media or components for transmission media; For most purposes, however, they are to be understood. However, this description is to be understood in such a way that a lubricant or transfer agent according to the invention may contain other oils and additives, such as an anti-foaming agent, in addition to the listed phthenic and branched paraffinic ingredients (or their fluorine substitution products) phosphorus-containing agent for improving the slip properties, an agent for improving the viscosity index (e.g., high molecular weight polyisobutylene), a pour point depressant (e.g., a fluorine-containing saturated polyolefin), a corrosion inhibitor (e.g. of the alkylene glycol laboratory salt type ), an antioxidant and a sludge dispersant. A particularly valuable additive, which combines effects as a detergent, corrosion inhibitor and as an agent for improving the sliding properties at high speed, is a magnesium, calcium or barium salt, in particular an overbased salt, a weak acid or a partial ester of a weak acid, such as thiophosphoric acids, phenols, phosphoric acid diesters, sulfonated alkyl aromatic hydrocarbons and the like. Examples of these are overbased salts of dithiophosphoric acid, calcium alkylphenates and calcium salts of mahoganyic acids. Additives, the addition of which to the hydrocarbon base according to the invention should be avoided, are compounds with long straight-chain or weakly branched alkyl celts and / or strongly polar groups, such as C ₁₂ - to C ₂₀ -alkylamines and dibutyl phosphite. In general, suitable additives are characterized by a friction ratio, at 182.9 m / min, (or above of more than 0.8), preferably more than 0.9.

Power transmission fluids are important components of speed converter systems using a traction drive or a friction clutch work. In particular, the transmission fluids according to the invention are suitable for traction transmissions, as described in the following United States patents and publications will:

1867 553, 3 006 206, 3 225 617,
2 549 377, 3 115 049, 3 268 041,
2 871 714, 3 184 990, 3 301 364.

Kraus, C. E., ASME - Paper 65 - MD-30 (New York, N.Y. Meeting, May 17-20, 1956).

He wk o, L. O "AIAA- Paper 67-429 (AIAA 3rd Propulsion Joint Specialist Conference, Washington D. C, July 17-21, 1967).

Although there is no known possibility from the structure or other chemical factors to deduce whether a particular fluid is satisfactory as a lubricant or transfer agent suitable in a traction drive; However, there is the possibility of indicating suitability ■ ils transmission medium to examine a liquid with the help of devices and methods as they in U.S. Patent 2,045,555 or by F. G. Rounds, Journal of C & E Datam Vol. 5, No. 4, Pp. 499 to 507 (1960) and ASLE Transactions, Vol. 7, pp. 11 to 23 (1964). Of special The research traction device according to L. O. Hew kο et al in “Proceedings of the Symposium on Rolling Contact Phenomena ", pp. 157-185 (1962), Elsevier, Amsterdam, Netherlands.

It has been found according to the invention that liquid naphthenes having 16 to 40 carbon atoms, which as Basic structure have a di (cyclohexyl) alkane or a hydrindane radical, are particularly good as Lubricant for friction or traction drives with fixed or variable conversion ratio suitable.

It has also been found that a particularly valuable power transmission system comprises a stepped roller or continuously variable transmission and lubricating and transmitting means therefor comprising a lubricating oil-based hydrocarbon base with an ultraviolet absorption at 26 millimicrons (260 UVA) less than zero , 5, which preferably contains at least 10 percent by weight of a C ₁₁ to C ₂ 7 hydrindane. The use of a hydrocarbon-based lubricant comprising 35 volume percent 1,1,3-trimethyl-3-cyclohexylhydrindane (often referred to as DMMCHH), 5 volume percent 2,5- (dicyclohexyl) -2-methylpentane (DCHMP), and 50 volume percent of a polyisobutylene oil with a viscosity of 5 cSt at 98.89 ° C, containing 33% recurring units with geminal dimethyl configuration, as a lubricant and transmission agent for a roller gear working in stages, it allows, for example, that the power transmission system formed works with twice the speed throughput compared with Power transmission systems using the best known fluids (naphthenic mineral oils).

It was also found that liquid C ₁ , - to C ₄₀ -naphthenes with a spirodecane, spiropentane, perhydrofluorene, perhydrobiphenyl, perhydroterphenyl, decalin, norbornane, perhydroindacen. Perhydrohomotetraphthen-, Perhydroacenaphthen-, Perhydrophcnanthren-, Perhydrocrysen-. Perhydroindane - 1 - spirocyclohexane, perhydrocarylophyllene-. Pinane, camphane, perhydrophenylnaphthalene or perhydropyrene residue. as a basic structure. are excellent lubricants and transmission agents for power transmissions.

In a new and advantageous one explained in more detail later Embodiment of the invention it has been found that certain adamantane hydrocarbons and their fluorine, ether or ester derivatives as transfer liquids or components of transmission fluids are valuable. In general, good traction properties appear characteristic for compounds with the adamantane core or for naphthenes or alkyl or cycloalkyl naphthenes that can be converted into adamantanes. Due to a particularly good combination of Traction properties, the degree of fluidity at 98.89 ° C and low temperature properties, however preferred as perhydroaromatic compounds are naphthenes containing the hydrindan, decalin. Perhydrophenous, Bicyclohexyl, Perhydrotcrphnyl-, Perhydroacenaphthcn, Adamanlan or Perhydrophenylenrest contain. Fluorine derivatives of these perhydroaromatics, in which an average of 1 to all hydrogen atoms of the hydrocarbon are replaced by fluorine are also considered to be the transfer fluid or components suitable for transfer fluids.

In general, naphthenes have a lower viscosity index (especially below one ASTM-Vl of 0, with the exception of compounds with a phenanthrene or adamantane basic structure) the higher traction coefficients. These naphthenes can be used alone or in a blend with additives, such as dispersants or antioxidants, or with certain described below Paraffinic hydrocarbons are used to improve the flowability properties of the obtained Change lubricant. Depending on the end use desired, this may Lubricant if it is liquid at room temperature

ίο is available as gas oil or, if it is solid, as bearing grease be used.

A preferred embodiment of the invention provides a power transmission system comprising a traction drive and as a lubricating and transmission medium therefor a composition comprising a predominantly above 260 ⁰ C lying hydrocarbon base having a kinematic viscosity at 98.89 ° C in the range of 1.5 to 200.0 (preferably 1.8 to 20) cSt. This hydrocarbon base contains a perhydrogenated trimer, dimer or codimer of

(1) styrene,

(2) u-methylstyrene,

(3) / i-methylstyrene or

(4) a derivative of these styrenes (1), (2) or substituted by one or two methyl radicals on the ring (3).

To avoid liquid losses, the boiling point of the base should preferably not be below the gas oil range, in particular the base should boil in the lubricating oil range. The ülbasis should generally have predominantly at about 260 ^c C and preferably predominantly boiling above 315.56 ° C (with the exception of fats) has a 90% share below 510 ° C. The distillation of such products is preferably carried out at reduced pressure (e.g. below 5 mm of mercury), including with the aid of vacuum-steam distillation, in order to avoid thermal decomposition.

The monomer-free perhydrogenated reaction products according to the invention usually contain components which boil predominantly in the range from 100 to 250 ° C. at 0.5 mm Hg, and the proportion selected for a specific base is obtained by vacuum distillation in the form of a fraction with the desired viscosity and the desired flash point . Preferably, the flash point is above 71.11 ⁰ C and in particular above 121.1 TC. The viscosity and / or the viscosity index of the oils according to the invention can also be adjusted by adding fixed amounts of light (low-boiling) components and heavier (higher-boiling) components.

Particularly valuable components of oils with a higher viscosity are the perhydrated trimer or tetrameric products corresponding naphthenes, which are normally in smaller proportions in the According to the invention, perhydrogenated styrene dimers are present, which, however, are present in distillation residues or can be enriched in fractions boiling predominantly above 323.89 ° C. These trimers and tetramers can also be produced in high yield by further polymerization of the dimerisate before perhydration, in particular by polymerizing the dimerizate with additional monomers will.

The perhydrogenated dimer or codimer, sometimes referred to below as "hydimer", can preferably consist predominantly of a C ₁₆ to C ₂₂ cyclohexylhydrindane or a C ₁₂ to C ₂ g di (cyclohexyl) alkane and is usually a mixture of isomers of both structures The naphthenes mentioned have the following structural formulas:

Di (cyclohexyl) alkane

Cyclohexylhydrindane

where η 1 to 3, R ₁ and R ₂ hydrogen atoms or methyl radicals, R ₃ , R ₄ , R ₅ , R ₆ and R ₇ hydrogen atoms, methyl radicals, ethyl or isopropyl radicals, R ₁ 'a methyl or ethyl radical and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and Rg represent hydrogen atoms or methyl radicals. For example, 209 g (239 ml) // - methylstyrene _{can be polymerized with 7 ml H 3} PO ₄ -BF ₃ to form a caramel-like reaction product, which is predominantly at 315.56 to 323.9 "C with one atmosphere (120 to 125 ° C at 0.75 mm Hg) and consists mainly of a dimer of the following structure:

line, phenanthrenes, acenaphthenes, indacenes, hydrindacenes, Contain fluorene, phenylindane, phenylhydrindane and phenylalkylcyclohexyl compounds. In In some cases such aromatic compounds can be valuable as they are used to dissolve certain additives contribute in the liquid. However, in order to reduce the traction coefficient in a friction drive To avoid extreme working conditions present, it is preferred to use a hydrocarbon base to use that are essentially free of olefinic and aromatic unsaturations Bonds is, as indicated by an ultraviolet absorption at 260 πΐμ (260 UVA) of less than 0.1 and one Iodine number of less than 2 is occupied.

When the hydrocarbon base according to the invention consists essentially of naphthenes which correspond to perhydrogenated styrene trimers or dimers or their alkyl derivatives, this base has a low viscosity index and therefore poor low temperature properties such as dropping point. It has surprisingly been found that new transmission fluids with a traction coefficient at least 10% higher than that of DMAP at 182.9 m / min at 93.33 ° C and 28,123 kg / cm ² and with an ASTM viscosity index greater than that than 40, can be prepared by mixing certain branched paraffinic hydrocarbons with the perhydrogenated liquid dimeric or trimeric styrenes.

Surprisingly, it has been found that particularly effective power transmission systems are those which, as a lubricant and transmission medium for a frictional power drive, have a hydrocarbon base with a UV absorption at 260 πΐμ of less than 0.5 and which have at least one substituted C ₁ , - to C ₂₂ -Cyclohexylhydrindane contain the structure mentioned.

This hydrindan should be present in a proportion of at least 5 percent by weight, based on the base, together with 0.1 to 20 percent by weight, based on hydrindan, of a branched paraffin which is a completely hydrogenated, liquid polymer, copolymer or terpolymer of a C ₄ - , C ₅ -, C "- or C ₇ -olefins. Such olefins are preferably isobutylene, 3-methylbutene-1, 4-methylpentene-1 or 2,3-dimethylbutene-1. It is particularly advantageous if at least 33% (in particular 90 to 100%) of the repeating units (with the exception of the terminal methyl groups) of this olefin polymer have the structure

In a range from 323.9 to 448.9 ° C (125-225 ⁰ C at 0.75 ram) boiling fraction (45 g) were also the trimers and tetramers vorgefun the.

A hydrocarbon base according to the invention with an initial traction coefficient greater than that of 1,3- (5,7-dimethyl) adamantyl dipclargonate (DMAP) at 182.9 m / min per 28,123 kg / cm ² can also in addition to the perhydrated dimers, trimers and tetramers up to 10 percent by weight of aromatic compounds, such as naphtha

55

C-

wherein R ₁ "is a hydrogen atom or a methyl radical and R ₂ 'is an isopropyl or isobutyl _{radical when R 1} " is a hydrogen atom and R ₂ "is a methyl, ethyl, isopropyl or isobutyl radical when R ₁ "is a methyl radical. Compounds in which the average number of branches per molecule is greater than 3 are also preferred. (The geminal configuration is considered to be two branches.)

For example, the olefin polymer can be an average Have molecular weight from 170 to 1000 when at least 33% and preferably at least 50% of the repeating units of the polymer (excluding the end groups) the following Have structure:

For example, the following hydrindanes can be used:

CH,

CH ₃

C-

Particular advantages in connection with such a paraffin, a polyisobutylene or a Corresponds to copolymers or terpolymers of isobutylene with other butenes, has a medium that as hydrindane the isomers of l-methyl-3-cyclohexylhydrindane or!,!, S-trimethyl-S-cyclohexylhydrindane or mixtures of these compounds.

The nuclear magnetic resonance spectrum (NMR) of the particularly preferred, highly geminal branched paraffin oil has a band caused by the hindered methylene group at about 8.58 τ which is larger than the band caused by unhindered methylene groups (at about 8.85 τ). Branched paraffin oils with such a high degree of methylene groups restricted by neighboring groups and a lower degree of unhindered methylene groups do not become significant Part found in refined naphthenic or paraffinic petroleum.

The new hydrocarbon base, which contains a mixture of at least one Cj ₆ - to C ₄₀ naphthene and at least one branched paraffin, preferably has a viscosity in the range from 1.8 to 20, OcSt at 98.89 ° C., a viscosity temperature -Function VI greater than 40 and a traction coefficient that is at least 10% greater than that of DMAP at 182.9 m / min at 93.33 ° C and 28 123Vg / cm ² . Of particular value is such a hydrocarbon base which contains 5 to 50 percent by weight of the isomers of I, I, S-trimethyl-S-cyclohexylhydrindane and 1 to 18 parts by weight of an isobutylene polymer or copolymer per part by weight of the hydrindane.

In addition to the branched paraffin or instead of the branched paraffin, the hydrocarbon base according to the invention can also contain _{2 to 25 percent by weight of C 16} to C _{22 alkylhydrindanes of the following structural formula to improve the viscosity index:}

R ₁

In this formula, the radicals R ₁ , R ₂ , R ₃ and R _{4 represent} hydrogen atoms and cyclic and acyclic paraffinic radicals having 1 to 12 carbon atoms. So can

Hydrindane boiling point
° C at
0.5 mm Kinematic
viscosity
(cSt)
at 98.89 ° C ASTM
D 2270 Vl 2-n-decylhydrindane
5-decylhydrindane ...
2-n-butyl-1 -n-hexyl-
hydrindan
5-n-butyl-6-n-hexyl-
hydrindan
2-n-butyl-5-n-hexyl-
hydrindan 129
130
119
119
123 2.50
2.43
2.36
2.18
2.28 49
150
63
88
131

The perhydrogenated OH-gomers of styrene, u-methylstyrene, β-methylstyrene and their mono- and dimethyl ring-substituted derivatives suitable according to the invention can be obtained by customary addition polymerization and subsequent high-pressure hydrogenation.
The polymerization can be carried out under such conditions that the polymer mixture obtained consists primarily of the desired dimer and a small proportion of the trimer and other by-products. On the other hand, the polymerization can be carried out under such conditions that a high molecular weight semisolid or even a solid polymer is formed and the resulting high polymer is then, for example, by thermal cracking (preferably under reduced pressure), dcpolymerized to an oil which consists of the desired dimer or a mixture of dimers and other by-products such as trimers. For example, the oil obtained by thermal depolymerization at reduced pressure from high molecular weight poly ((i-methylstyrene)) contains a small amount of a trimer of the hydrindane type with a molecular weight of 354 and having the following structure:

oils of a predominant portion of this trimers can be obtained by distillation of poly (a-methylstyrene) oils, which contain a boiling range from about 329.5 to 496 ⁰ C fraction. Trimers of this structure type are sometimes referred to below as "hydrindane trimers" and the abovementioned trimers are sometimes referred to as "HTAMS-H" (hydrogenated trimeric "methylstyrene with hydrindane as a structural unit). The other structural types of polymeric styrenes are sometimes referred to below as "poly (alkylcyclohexane)" or as follows: "Cycloxane trimers," the poly-

2372

mers with three structural units, "HTAMS", the hydrogenated trimers of u-methylstyro], which do not have any Contain hydrindane as a structural unit.

After perhydration, this trimer has a viscosity of about 12OcSt at 98.89 "C, a boiling point of about 230 ⁰ C at 0.2 mm mercury (or about 487.78 ° C for one atmosphere) and is a valuable component for the hydrocarbon base oils of the invention for which high viscosity is desired This trimer is also valuable as an additive for increasing the average traction coefficient of a hydrocarbon traction fluid, as will be illustrated later (Table III).

A polymerization product that still contains a larger proportion of this trimer and next to it as a second and main component!, l-DimethyW-methyl-S-phenylindane is made by polymerizing u-methylslyrole in the presence of aluminum chloride formed as a catalyst.

An essentially trimer-free dimerization product of u-methylstyrene is obtained by reaction of cumene with ferric chloride. This reaction leads to l, l, 3-trimethyl-3-phenylindane as the only one Main product in addition to a small amount of the saturated form of the dimer of α-methylstyrene, which itself has a terminal double bond. This compound is 2- (p-cumyl) -2-phenylpropane (a polyalkylcyclohexane) of the following structure:

CH ₃
C.

// V

CH,

CH ₃

CH

CH ₃

35

According to a particular embodiment of the invention, the power transmission fluid can be dimers with a di (cyclohexyl) alkane structure, such as perhydrogenated 2- (p-cumyl) -2-phenylpropane odcr 2,5- (Dicyclohexyl) -2-methylpcntane or naphthenes, which contain the dicyclohexane residue as a structural framework have, such as naphthenes of the following structure:

CH ₃

C-H

45

5 °

CH ₃ -C- CH ₃
H

55

alkanes or dicyclohexanes have the following structural formula:

A new and preferred type of such a hydrocarbon base, which is particularly valuable as a lubricant for a traction drive, has a viscosity-temperature function Vl greater than 40 and a traction coefficient greater than that of DMAP at 182.9 m / min 93.33 ° C and 28 123 kg / cm ² . This hydrocarbon base contains a C ₁₄ to C ₃₆ di (cyclohexyl) alkane or dicyclohexane with a freezing temperature below -30 ° C and 0.1 to 20 parts by weight, based on the total naphthene content of the base, at least one fully hydrogenated, synthetic, liquid Polymers, copolymers or terpolymers of C ₄ to C ₈ olefins. The mentioned di (cyclohexyl) -R,

in which η is 0 to 4 and the radicals R 1 to R _{8 are} hydrogen atoms, methyl, ethyl, n-propyl or isopropyl radicals.

In either case, the ultimate perhydrogenated styrene dimer should be (Hydimer) to be as largely free of aromatic and olefinic unsaturation as it is economically justifiable. Small proportions of such unsaturated compounds can be hydrogenated from this Oligomers with the help of an adsorbent such as silica gel, acidic activated clay or be removed with the help of a crystalline zeolitic molecular sieve (sodium zeolite Y).

The perhydrogenated dinieres preferred according to the invention, cycloalkylhydrindane, can also be prepared by the Ipatieff-Pines process. Any of the cycloalkyl - perhydroindan - hydrocarbons (preferably 3 to 20) have a kinematic viscosity at 98.89 ° C ranging from 1.5 to 200.0 cSt and boiling above 200 ⁰ C and below about 500 ⁰ C at one atmosphere, are well suited as lubricants for a speed converter with friction drive, especially if this hydrindane is present as a component of a hydrocarbon base, which is also made by hydrogenating a liquid synthetic polymer, copolymer or terpolymer of a C ₄ , C ₅ , C ₁ , or Contains liquid paraffin oil obtained from C _{7 olefins (e.g. polyisobutylene).} Preferably the branched paraffin has more than three branches per molecule. The hydrocarbon base according to the invention can also contain mixtures of cycloalkyl-perhydroindane hydrocarbons (including other alkylhydroindane), such as compounds obtained by hydrogenating catalytic gas oil fractions predominantly boiling above 273.9 "C or by alkylating these fractions with olefinic C ₂ - to C ₁₀ - (preferably C ₃ - and C ₄ -) hydrocarbons and subsequent hydrogenation were obtained.

Di (cyclohexyl) alkane suitable as constituents of the hydrocarbon base according to the invention can also be prepared by radical or anionic polymerization of styrenes. Particularly valuable for the invention is 1- (4-Mcthylcyclohexyl) -1 - (2-methyl-5-isobutylcyclohexyl) -2-methylpropane (C ₂₂ H ₄₂ ) of the structure

H
CH ₃ - C - CH ₃

CH ₂ - C - CH
CH ₃

2372

■ >>

ΛιιΓ reason of the high traction coefficient and Its good stability in the case of long-term use in a transmission is one that is invented Hydrocarbon base boiling substantially above 260 "C and a viscosity of more than 3 cSt at 98.89 "C and reveals a naphthene which is a perhydrated dinning or codiming of styrene, «-methylstyrene, // - methylslyrole or theirs corresponds to mono- or dimethylringsubslituicrlcn derivatives, valuable as a lubricant and transmission medium for power transmissions. Such a power transmission system However, it is limited to uses that do not involve lower temperatures occur as about -17.8 "C, as in submarines or warships or in industrial power transmissions, in buildings with a temperature above about -17.8 and preferably above about 4.4 "C. Temperature. Such a lubricant can of course also be used in a temperature lower than that Can be used as a -17.8 "C exposed power train if the oil is kept at a higher temperature (e.g. by a heater).

For use at low temperatures and when applying extremely high liquid wedge pressures (e.g. in external submarine transmissions with pressure compensation) a force transmission fluid with a viscosity of less than 2 cSt at 98.89 ° C and a slightly lower traction coefficient to be useful. Examples of such low-viscosity liquids are the oils U, Z, AC and AD in Table III.

In automatic automotive sleeveless drives, the weight, cost, and simplicity of the device are paramount, and temperatures as low as -40 ° C are contemplated. In this case, it is preferred that the lubricant used for the automotive transmission not no longer has a viscosity of greater than about -28.89 700OcSt at ⁰ C and a pour point of as about -40 C ^u. Such a transmission medium must therefore have a high viscosity index (preferably above 400 VTF-VI and in particular above 75) and a viscosity at 98.89 ° C. in the range from 3 to 15 cSt.

Paraffin oils with a high proportion of recurring units in the general structural formula

R ₁ "
C-

C-

R ₂ "

where R ₁ "is a hydrogen atom or a methyl radical and R ₂ 'is an isopropyl or isobutyl _{radical when R 1} " is a hydrogen atom, and RV is a methyl, ethyl, isopropyl or isobutyl _{radical when R 1} "is a methyl radical means, have a higher traction coefficient for a given viscosity index than the other paraffin oils.

One embodiment of the invention therefore relates to one in a power transmission system a traction drive as a lubricant medium used on a hydrocarbon basis with a kinematic viscosity at 98.89 ° C in the range 1.8 to 20.0 cSt. This medium contains at least a branched paraffin, its repeating units at least 33% the structure

I H

- C C ■

I H

have, wherein R _{1 is} a WasserstolTalom or a methyl group and R _{2 is} an isopropyl or isobutyl radical. The average number of branches per molecule is preferably more than 3 (isopropyl or isobutyl radicals R _{2 being} regarded as two branches). These highly branched paraffins are not found to any significant extent in refined petroleum. Such a power transmission system is particularly advantageous when the branched paraffin has a pour point below 0 "C and an average molecular weight in the range from 188 to 560. Preferably at least 90% of the repeating units, with the exception of the end groups of the branched paraffin, have the structure given above. In a particularly preferred embodiment of the invention, the power transmission fluid contains at least one branched paraffin in which the radical Ri is a hydrogen atom when R _{2 is} an isobutyl radical, and the radical R _{2 is} an isobutyl _{radical when R 1 is} a methyl radical (oils 7 and 9).

When comparing the "Hydimer" oils (oils 5 and 14) it can be seen that the oil with the higher The proportion of oligomers of hydrindane type (oil 5) has a higher average traction coefficient 304.8 m / sec and a higher viscosity-temperature function Vl than the hydimer oil (oil 14) with a has a higher proportion of di- (cyclohexyl) structure.

New power transmission fluids can be created by blending naphthenic and branched paraffinic Hydrocarbons are produced. The blended power transmission medium thus obtained has better traction properties than any of the components. For example, it was found that by mixing at least one hydimer oil with at least one branched paraffin oil (e.g. perhydrogenated Polyisobutylene) with a high proportion of recurring units of the structural formula mentioned

R ₁ "
C.

R "

H
C.
H

oils with good traction coefficients and good Viscosity index can be obtained.

Table I lists the primary structural units and / or processes contained in certain oils Manufacture of these oils listed. In Table_II are certain properties of the oils tested, including those obtained by the method of F. G. Rounds ir Journal of C&E Data, traction coefficients tested under various conditions In this tensile test, 1% DBCP (dibutyl paracresol) was added as an antioxidant to each oil.

The present as a constituent of the mixtures according to the invention is preferably branched Paraffin has a relatively low boiling point (the bc indicates a very uniform molecular weight). egg

is also preferred to use oils that Hydrogenation of an olefin polymer produced by Ziegler-Katulyse or by thermal cracking of a highly polymerized olefin were obtained, in the second place are prepared by acid catalysis Polymers and, in the third place of choice, polymers obtained by rudical catalysis are used, Im this is generally used as a component according to the invention preferred branched paraffin by polymerizing an olefin such as isobutylene, for example with a Ziegler catalyst, a fairly high molecular weight polymer is formed, that is highly viscous or even gel-like at room temperature. This high polymer is under Formation of an oil of the desired viscosity thermally cracked and this product obtained then fully hydrogenated to a branched paraffin oil which, in the case of isobutylene, is highly geminal Has disubstitution or geminal branching. Though by polymerization, distillation and hydrogenation, a similar oil can be produced, is obtained by the process according to the invention by polymerizing to a higher than desired degree and then thermal Columns (especially at reduced pressure) to an oil of the desired viscosity and a natural boiling range, a more uniform product with a 33% higher yield. Optional can use suitable branched paraffin oils instead of thermal cracking and subsequent strong hydrogenation obtained by hydrocracking a viscous olefin polymer.

According to the invention, oils with a high degree of geminal dimethyl branching are preferred, such as that by thermal cracking and subsequent hydrogenation of a high molecular weight, at lower Temperature-polymerized polyisobutylenes produced polyisobutylene oil, which is the most regularly repeating Has isobutylene structure. The oils produced by this thermal cracking have nuclear magnetic properties Resonance spectra that differ from the spectra obtained by high temperature polymerization differentiate produced oils. Fractions with a narrow boiling range resulting from such thermal Cracked oils separated have viscosity indices from 90 to 110.

An advantageous embodiment of the invention therefore comprises as a lubricating or transfer fluid for a power transmission a mass that is a hydrocarbon base with a kinematic viscosity at 98.89 ° C in the range from 1.5 to 200, OcSt which is a fully saturated isobutylene oil with a molecular weight of 200 to 1000, a pour point of below - 17.78 ° C, an ASTM viscosity index greater than 90, which is free of distillate fractions with a Vl of less than 80 and according to the NMR spectrum, 60 to 100% regularly recurring isobutylene units with a geminal dimethyl structure. The NMR spectrum of such an oil shows a strong band at about 8.58 r.

Oils derived from highly polymerized, stereoregular isobutylenes (i.e., polyisobutylene with a high Degree of hindered methylene groups, expressed by the band at 8.58 τ) due to thermal degradation can be produced under reduced pressure, forming new synthetic branched Paraffin oils are used, which are particularly valuable as components of power transmission fluids are, The unexpected valuable properties of the new polyisobutene cannula are made clear by the comparison those listed for oil D with door oil P in table 111 Properties clear, oil D is a mixture of 30% of a perhydrogenated dimerisate of u-methylstyrene and 70% oil 34 (of a polyisobutylene obtained by thermal cleavage with a highly stereoregular cr Arrangement), oil P contains 30% of the same hydimer oil and 70% oil S, one corresponding to oil 19 Oil which is a butylenes mixed by hydrogenating the polymerization product in the presence oil obtained from acidic catalysts, oil D, which is the new, hydrogenated polyisobutylene oil with a stereoregular arrangement of the repeating units contains, has an average traction coefficient at 304.8 m / min, which increases by almost 18% is higher than that of the oil P containing the hydrogenated mixed polyisobutylene.

The NMR spectrum of oil 34 is very different from that of oil 19 (or oil S). That is how it shows oil 34, the hydrogenated polyisobutylene obtained by cracking has a strong NMR band at about 8.58 τ and almost no band at 8.84 to 8.85 τ. A band at about 8.58 τ shows maximum hindrance of the methylene groups and a band at 8.84 to 8.85 τ indicates unhindered methylene groups in association with a branched chain.

Oil J shown in Table III is a new oil made by blending a hydrogenated polyisobutylene oil (Oil 34) with a strong band at 8.5S τ and almost no band at 8.84 to 8.85 τ with Oil S, obtained by hydrogenating the oil produced by acidic polymerization of mixed butylenes and having little or no band at 8.58 τ and a strong band at 8.84 to 8.85 r. These new blended oils and a power transmission system containing these oils represent another preferred embodiment of the invention. They are particularly valuable when _{blended with a hydrogenated mineral oil or with a C 13} to C ₄₀ naphthene.

On distillation, oil 19 shows a rather broad one Boiling range (243.3 to 565.5 ° C), and there are considerable proportions of higher boiling (10% above 560 ° C) and lower-boiling fractions obtained. The viscosity indices of the individual distillate fractions are considerably lower than the VI of the total oil. It can be seen from this that the viscosity index von Öl 19 is the result of the well-known "dumbbell blending" process is.

Even after hydrogenation, such a mixed polybutylene oil with a low degree of geminal branching is with a wide boiling range and a viscosity index achieved by dumbbell blending not as good as a component of a mixed paraffinic-naphthenic power transmission fluid such as the hydrogenated, cracked polyisobutylene of the present invention. This is done, for example, by a Comparison of oil 13 (a blend that is under Use of a polybutylene oil with a wide boiling range and a low degree of geminal branching was obtained) with oil 1, a blended oil that has the same proportion of one within narrow limits contains the boiling fraction of an isobutylene oil with more than 90% geminal branching.

A comparison of oil 37, a polyisobutylene fraction with a narrow boiling range, with oil 45, which is wider

H I 806 401

19 20

boiling fraction from which oil 37 was obtained, the mixture contains a C ₁₂ - to C ₂₀ -decalin,

Tends that the fraction boiling within narrow limits, which as a substituent at least one of the radicals

In comparison with the starting _{oil, a strongly differing C 1} - to C ₅ -alkyl, C ₅ - to Q. -cycloalkyl, C "- to

has additional traction coefficients. Thus, Cm-alkylcyclohexyl-, alkylcyclopentyl- showed. Bci-

For example, oil 37 has a 17% higher trac- 5, for example, alkylnaphthalenes (including

ionic coefficients at 304.8 m / min, at 93.3 ° C and hydrocarbon base fluids containing such alkyl

35 153 kg / cm ² , as the starting oil, contained in the naphthalenes of the invention) by strong hydrogenation

appropriate blends of naphthene and branched hydrogen pressure of more than 70.3 kg / cm ² ,

paraffinic hydrocarbons should preferably be more than 105.5 kg / cm ² , and in particular

each component and especially the branched io dere from 311 to 703 kg / cm ² , into an alkyl decalinc

Paraffin have such a narrow boiling range, can be transferred containing base liquid ,

than it is economically or technically justifiable. The decalin liquid obtained can contain up to 10%

Another highly stereoregular branched paraf- should contain the remaining aromatics (as a gel)

(in, which is used as power transmission fluid or in which, however, preferably less than 1% gel-like flavor

Blends according to the invention are used 15 maten, based on the decalin, and contain one

can, by hydrogenating an isobutylenepoly- UV absorption at 260 ΐΏμ of less than 0.1.

Produce mers, which by polymerization of 98 point. Such transmission fluids, the deca-

until 100% isobutylene was obtained. The average-line included show a better combination of

The molecular weight of the polymer can be determined by flow properties and traction properties and

Controlling the polymerization temperature set will have a longer effective service life at their

den, or a high molecular weight product can be used in traction drives as the alkyl

Formation of a low molecular weight polymer thermally naphthalene liquid wedges of the patents mentioned

be split. One such decalin is Tetraisopropyldekalin (TTI PD),

For the preparation of the paraffin according to the invention, the properties of which are listed in Tables 1, II and III with a high degree of geminal dimethyl branching (oils 17, 11, 21, G and AA).
A new and advantageous type of such a polyisobutylene and subsequent hydrogenation is a hydrocarbon base, which is preferred as a lubricant for an isobutylene polymer, which is valuable in a Mole traction drive, shows a Staudinger viscosity / weight of about 15,000 temperature functionVl over 40 and has a Trakbis of about 27,000 (that is, it is present in the viscous, semisolid, tacky state that is greater than that of DMAP's plastic, tacky, semi-solid state). At 182.9 m / min, at 28 123 kg / cm ² and 93.33 ° C, the oils according to the invention can, however, also pass through and contain such a decalin with a freeze-thermal degradation of higher polymer butylenes or temperatures below -30 ° C, as well 0.1 to 20 weight of lower molecular weight polyisobutylene oils with parts, based on the total naphthene content of the molecular weights of about 1000 to 15,000, at least one fully hydrogenated. thetic, liquid polymers, copolymers or

Other oils that can be used as power transmission fluid terpolymers of a C ₃ to C ₈ olefin.
A particularly valuable hydrocarbon base fluids (in particular as the third component for a transmission fluid can be obtained by strong mixtures according to the invention of perhydrated sty- 40 hydrogenation of a raffinate component, rol polymers [perhymer] and branched paraffins) which have a high content Acquire alkylnaphthalenes by perhydrating the mixtures.

As-hydrindacenes and indanylphenylalkanes produce higher-boiling and more viscous liquids which are obtained when indanes are obtained in liquid form from the higher-boiling hydrocarbon phase at 10 to 110 ° C with HF and BF ₃ in Beruh- 45 or from a dimethylnaphthalene brings abstinence. For example, indane can be produced with a C ₂ - to C ₅ -monoolefin (3-phenylpropane with HF and BF ₃ For example, in the presence of an HF · BF ₃ catalyst, the lower boiling points are preferably removed before the hydrogenation. One component, e.g. B. benzene and unreacted In- 50 particularly suitable hydrocarbon content for this dan, before perhydrogenation by distillation. On alkylation is a fraction with a high similarity being a valuable constituent content of 2,4-dimethylnaphthalene. As a residue of blended transfer liquids through Perhy- remaining aromatics can be prepared with the help of adsorption of the reaction mixtures, the hydrogenated raffinate fraction by means of a zeolite molecular sieve contacting octahydroanthracene or silica gel from a decaline-containing octahydrophenanthrene with an acidic catalyst be removed,
such as HF · BF ₃ or a crystalline zeolite catalyst. According to a further embodiment, the substitute can be obtained. found that both the traction

Another valuable third component of the properties as well as the flow properties is ge-naphthene and branched paraffins containing 60 common mineral oils, usually 15 to 60 media contains a perhydrogenated poly-1-octene oil with a weight percentage of gel-like aromatics, or Viscosity-temperature function VI above 80, before the usual hydrogenation and / or with acid over 100, which is added in a proportion of 5 to 50% traded and / or solvent-treated naph will. then oils (which contain as little as 5% gel-like aromatics

Another valuable embodiment of the preservation 65), through strongly hydrogenating refining,

discovery is a lubricating or transfer fluid which reduces or removes aroma

whose hydrocarbon base is a kinematic matic hydrocarbons in these oils

acts in the range of 1.5 to 200.0 cSt at 98.89 ° C, can be improved. This execution

to

The form of the invention is in contrast to the teachings of the art that hydrogenation is minor or no influence on the traction characteristics of naphthenic hat.

However, it has not yet been recognized that although the usual hydrogenating treatment is no or one has little influence on the intrinsic properties of a naphthenic oil, but that the traction properties can be noticeably improved if such a strong hydrogenation is carried out that an actual Removal of the aromatic hydrocarbons in the obtained hydrogenated oil occurs, the improvement the traction property is probably due to the type of cup in which the Aromatics are converted. This embodiment of the invention is shown in Tables 1,11 and III by comparing oils 12, 18, 22, 24, 27, 30, 33, 35, 36, 50, 51, I and AB illustrated.

A comparison of oil 23 with oil 19 shows also found that by hydrogenation of a polybulene oil (up to an iodine number of less than 2) the average traklion coefficient is improved.

Oil 36, for example, represents a naphthenic Distillate made using a suH'idierle Nickel molybdenum oxide on a catalyst containing aluminum oxide at a hydrogen pressure of 70.3 at with a freshly added liquid feed hourly space velocity of 0.5 and an hourly space velocity of the liquid recycle portion of 3.5, hydrogenating at 343.3 "C is refined. Strong hydrogenation of this oil, which has already been refined under hydrogenation, is produced Ol 27, which has a higher viscosity index and a noticeably improved traction coefficient owns. This strong hydrogenation can at a hydrogen pressure of 210.9 at for 6 hours in one Autoclave using a Raney nickel catalyst and subsequent adsorption on silica gel to remove remaining aromatics (about 1%) respectively. Instead of Raney nickel, platinum or Aluminum oxide can be used with the same result.

When using the naphthenic oils hydrogenated under severe conditions as the transfer fluid or as a constituent of a transfer fluid, it is preferred that these oils be less than 1% more aromatic Contains hydrocarbons (as a gel).

One embodiment of the invention relates to a lubricant for a traction drive that is based on hydrocarbons with a kinematic viscosity of 1.5 to 200, OcSt. The hydrocarbon base contains a naphthenic oil with a content of less than 1% of aromatic hydrocarbons. Preferably the naphthenic oil should be at 260 πΐμ a Exhibit ultraviolet absorption (260 UVA) less than 0.05, preferably less than 0.005. Characteristic for such hydrogenated naphthenic oils a viscosity at 37.78 "C can be in the range of so values as low as 30 SUS (Saybolt Universal Seconds) to values as high as 10,000 SUS can lie.

Another embodiment of the invention relates to a transmission medium door a traction drive which contains a fully hydrogenated or saturated naphthenic oil as described and 0.1 to 10 parts by weight, based on the naphthenic oil, of at least one fully hydrogenated, synthetic, liquid polymer, copolymer or terpolymer »! A (. '., - bis (' _H -oleline contains. The hydrogenated, liquid Olclinpolymea · reveals preferably at least 33% of the terminal, caused by dimethyl substitution, such as are present in polybutylene oils. Even more advantageous is a polyisiobutylene oil which is at least 90% and preferably 100% geminal dimethyl branches (excluding the end groups),
A comparison of the tables in Tables I! and III for oil 35

ίο (ASTM-ÖI Nr. 3, a Naphthcnschmicröl) and oil 30, which was produced by hydrogenation under strict conditions of oil 35 and subsequent removal of remaining aromatics by adsorption on silica gel, shows that the viscosity index of the strongly hydrogenated oil obtained is wide The main difference between the composition of naphthenic lubricating oil 35 and the naphthenic distillate used to produce oil 22 is that the naphthenic distillate contains 45% aromatic hydrocarbons (corresponding to 21% aromatic) before hydroraflination bonded carbon atom ^ ie C ₄ ). The proportion of aromatics remaining removed from the distillate hydrogenated under strict hedging conditions with the aid of silica gel is very low (less than 1%); the completely hydrogenated naphthenic distillate obtained therefore contains more than twice the proportion by weight of naphthenes (a total of about 70% naphthenically bonded carbon atoms compared with the conventionally hydrorefined naphlene oil.

At least 15 percent by weight, preferably more than 25 percent by weight of that in the naphthenic oils hydroraffinated according to the invention under strict conditions The naphthenes contained in the oil are created by perhydrating the oil originally, prior to hydrogenation, present aromatics.

In the context of the invention, therefore, a saturated naphthenic transfer liquid is produced by hydrogenation under severe conditions of a naphthene distillate or an acid refined or solvent refined one Naphthenic oil or a hydro-refined naphthenic distillate with a content of at least 10% gel-forming aromatic hydrocarbons and a kinematic viscosity less than 3.0, preferably less than 2.5 cSt at 98.89 "C. The hydrogenation is produced to a level less than 1% gel-like. Aromatics carried out. For example, that mentioned in Table II oil 50 by hydrorafinating under strict conditions a naphthene distillate containing 40% aromatics, which has a SUS value (at 37.78 "C) of 50 and a 260 UVA value of 5.4.

This highly hydrogenated light naphthenic distillate can also be mixed with perhydrogenated oligomer oils (such as the perhydrogenated trimers of u-methylstyrene with hydrin structure) blended as illustrated by oil 51 in Table II. The invention Oils contain more than 50% and preferably more than 75% naphthenic hydrocarbons and less than 2% aromatic hydrocarbons.

According to another embodiment of the invention, a napkin oil is used, which under has been hydrogenated under strict conditions. (The oil has a viscosity of 30 to 10,000 SUS at 93.33 ° C.) The naphthenic oil contains more than 50 percent by weight of naphthenic hydrocarbons and a few

(3

less than 1% aromatic hydrocarbons. This oil is then blended with 0.1 to 10 parts by weight, based on the perhydrogenated naphthene oil, of at least one fully hydrogenated, synthetic, liquid polymer, copolymer or terpolymer of a C _{4 to} C ₇ olefin. A particularly preferred branched paraffin oil is a polyisobutylene with a high proportion of recurring structural units with geminal dimethyl branching, in accordance with the formula already shown. This oil preferably shows a strong NMR band at about 8.58 τ.

Another embodiment of the invention relates to novel make-up fluids and power takes advantage of the discovery that the traction properties of branched paraffin oils with a low degree of geminal dimethyl branching (or with a strong NMR band at about 8.84 to 8.85 τ) can be improved by using a fully hydrogenated liquid isobutylene polymer mixed with a high proportion of recurring units with geminal dimethyl branching exists (indicated by a strong NMR band at around 8.58 τ). These blended oils can advantageously still be hydrogenated with 0.1 to 10 parts by weight of under severe conditions Naphthen distillates are blended.

It has also been found that liquid C _{18 to} C ₄₀ naphthenes which contain a perhydroterphenyl, or liquid C ₁₃ to C ₂₅ naphthenes which contain perhydrofluorene as the basic structure, can be used as lubricating and transfer fluids for stepless or stepless working Pull drives are suitable.

The invention therefore also relates to a lubricant which is particularly well suited for a power transmission system with a step transmission, roller transmission or with a continuously variable transmission. The lubricant mixture consists of a hydrocarbon base with a viscosity of 2.0 to 12 cSt at 98.89 ° C and an ultraviolet absorption at 260 ηΐμ (260 UVA) below 0.5, preferably below 0.1. According to the invention, this base contains at least 5, preferably at least 10 percent by weight of a C _{18 to} C ₂₆ perhydroterphenyl or of a C ₁₃ to C ₂₅ perhydrofluorene. For example, a power transmission system which comprises a roller drive working in stages and a hydrocarbon base as a lubricant, the 10 volume percent perhydrofluorene and 90 volume percent of a polyisobutylene oil with a viscosity of 5 cSt at 98.89 ° C, in which more than 33% of the repeating units present in the geminal dimethyl configuration contains, operate at a higher speed throughput than the use of the best naphthenic mineral oils allows.

In a preferred embodiment of the invention, a lubricating and power transmitting means is used in a Kraftumwandlungssyslem with friction drive, consisting of a predominantly above 260 ⁰ C boiling hydrocarbon base having a kinematic viscosity from 1.5 to 200.0, preferably 1.8 to 98 2OcSt , 89 ° C. According to the invention, this base contains perhydrogenated orthoterphenyl or perhydrofluorene or a saturated _{phenyl derivative substituted with C 19} to C 0 hydrocarbon radicals or a derivative of perhydrogenated fluorene substituted with hydrocarbon radicals, in which alkyl, cycloalkyl or alkylcycloalkyl radicals can be present as hydrocarbon radicals.

Perhydrofluoren (which has an ASTM viscosity index of 105, a kinematic viscosity at 98.89 ° C of 2.5 cSt and a pour point below 0 ° C) and its C ₁₇ to C ₂₃ alkyl substituted derivatives, e.g. B. the dimethyl derivative are just as suitable as components for transfer fluids as perhydroacenaphthylenes. Preferred perhydrogenated acenaphthylene and fluorene derivatives can be obtained by perhydrogenating the following fluorene compounds (or ίο their hydrogenation products):

1 - (5-acenaphthyl) butane,
1 - (5-acenaphthyl) hexane,
9-methyl fluorene,
9- (4-methylbenzylidene) fluorene,
9-phenyl fluorene,

1,8-dimethyl-9- (2-tolyl) fluorene,
9-benzylidene fluorene.

Preferred perhydrogenated terphenyl derivatives can be obtained by perhydrogenating orthoterphenyl (or hydrogenated orthoterphenyls), C ₁₉ to C ₂₄ methyl-substituted o-terphenyls or by hydrogenating hydrocarbon fractions which contain at least 5% o-terphenyl.

The monomer-free perhydrogenated terphenyl and fluorene compounds according to the invention are usually made from distillate fractions obtained from refining petroleum, for example from the circulating stream of catalytic cracking or the circulating stream of thermal demethylation of alkyl aromatic hydrocarbons. Satisfactory transmission fluids can be compiled from these perhydrogenated distillate fractions if the distillate fraction at least 5% (preferably at least 15%) terphenyl, fluorene, hydrofluorene or hydroterphenyl compounds contains.

When the hydrocarbon base according to the invention consists essentially of naphthenes corresponding to perhydrogenated terphenyl, fluorene or their alkyl and cycloalkyl derivatives, this base has a low viscosity index and therefore poor low temperature properties such as pour point. However, it has been found that new transmission fluids with a traction coefficient at least 10% greater than that of DMAP (at 182.9 m / min, at 93.33 ° C and 28,123 kg / cm ² ) and an ASTM - Viscosity index of more than 40, by blending 1 to 20 parts by weight of liquid branched paraffinic hydrocarbons with an average of more than three branches per chain with liquid C ₁₈ to C ₄₀ naphthenes containing perhydroterphenyl or perhydrofluorene radicals as the core structure.

It has surprisingly been found that a particularly advantageous power transmission system comprises a frictional power drive and, as a lubricant and transmission agent for this, an essentially saturated hydrocarbon base with a UV absorption below 0.5 to 260 πιμ, which contains at least one of the following compounds: Perhydröorthoterphenyl , C ₁₈ to C ₄₀ hydrocarbyl-substituted terphenyl derivatives, perhydrofluorene, C ₁₄ to C ₂₅ hydrocarbyl-substituted derivatives of perhydrofluorene, the perhydroterphenyl or pefhydrofluorene compound being present in an amount of at least 5 percent by weight, based on the base, and the also 0.1 to 20 parts by weight,

209 525/496

moved to the perhydrofluorene, a fully hydrogenated liquid polymer, copolymer or terpolymer of a C ₃ , C ₄ , C ₅ , C ₆ , C ₇ or C ₈ olefin. It is preferably a polymer of isobutylene, 3-methylbutene-1, 4-methylpentene-1 or 2,3-dimethylbutene-1. It is particularly advantageous if at least 35%, preferably 90 to 100%, of the repeating units (with the exception of the terminal methyl groups) of the olefin polymer have the structure

C-

in which R ₁ "denotes a hydrogen atom or a methyl radical and R2 'denotes an isopropyl or isobutyl radical when R ₁ " is a hydrogen atom, and R2' denotes a methyl, ethyl, isopropyl or isobutyl radical when R ₁ " stands for a methyl radical.

Another advantageous embodiment of the invention relates to the use of a lubricant and Hydrocarbon-based power transmission medium with a kinematic viscosity at 98.89 ° C im Range from 1.5 to 200, OcSt in a traction drive transmission system.

The hydrocarbon base contains a paraffin oil with an aromatics content of less than 1 percent by weight. The UV absorption at 260 πΐμ is below 0.5. Preferably, this paraffin oil is obtained by hydrogenating a mineral oil with more than 60% paraffinic carbon content (C _P ), more than 30% naphthenic carbon content (C _n ) and more than 2% aromatic carbon content (C _A ) under severe conditions. The paraffin oil preferably has an ASTM viscosity index greater than 80, a refractive index greater than 1.47 at 20 ° C, and a SUS viscosity in the range from 60 to 3000 at 37.78 ° C.

In another embodiment, the base contains 5 to 75% of a C ₁₃ to C ₄₀ naphthene with a glass transition temperature in the range from -90 to -30 ° C. This naphthene contains, as its core structure, a cyclohexylhydrindane, di (cyclohexyl) alkane, spirodecane, Spiropentane, perhydrofluoren, perhydrobiphenyl, perhydroterphenyl, decalin, norbornane, perhydroindacene, perhydrohomotetraphthen, perhydroacenaphthene, perhydrophenanthrenes, perhydrocrysen, perhydroindan-1-spirocyclohexane, perhydrocarylophyllene, perthalene, perhydrophylene, perhydrocarylophyllene, perthalene, perhydrophenaphylene, perhydrocarylophylene, perthalene, perhydrophenaphylene, perhydrocarylophyllene, perthalene, perhydrophylene, perhydrocarylophyllene, perthalene, perhydrophylene. Although the common paraffinic and naphthenic mineral oils contain some or all of the types of naphthen mentioned in small amounts, hardly more than 5% of each type is found in any mineral / lubricating oil. It is therefore advisable to analyze a paraffin oil of the type which can be used according to the invention, in particular to determine its content of said naphthenes and to add at least one compound from at least one of the said naphthene groups to this paraffin oil in such an amount that the traction coefficient is increased. The mean traction coefficient at 304.8 m / min should preferably be increased by at least 10% by this naphthenic additive.

Particularly preferred naphthenes which can be added are those which are perhydrated Polymers, copolymers or terpolymers of the following styrenes correspond:

(1) styrene,

(2) u-methylstyrene,

(3) / i-methylstyrene,

(4) a mono- or dimethyl ring-substituted one

Derivative of (1), (2) or (3).
10

The invention also covers power transmission systems which contain a paraffin oil and 1 to 10 parts by weight, based on the paraffin oil, of a completely hydrogenated, liquid polymer, copolymer or terpolymer of C ₃ to C ₈ olefins.

Another class of blend ingredients that can be blended with these paraffin oils or mixtures of these paraffin oils with naphthenes or branched paraffins preferred according to the invention is a rigorously hydrorefined naphthenic lube oil that is less than Contains 1% aromatic hydrocarbons and has a viscosity in the range of 30 to 10,000 SUS 37.78 ° C.

Oil I in Table III illustrates the benefits of a embodiment of the invention, namely a hydrocarbon base with a kinematic viscosity at 98.89 ° C in the range from 1.5 to 200, OcSt, which is a paraffin oil with less than 1 percent by weight Aromatics and a UV adsorption at 260 m μ of less than 0.5 and 5 to 75% of a naphthene contains which is a perhydrogenated polymer, copolymer or terpolymer of

(1) styrene,

(2) «-Methylstyrene,

(3) / i-methylstyrene and

(4) corresponds to a mono- or dimethyl ring-substituted derivative of the compounds (1), (2) or (3).

According to another embodiment, as a component of a blended power transmission fluid, which contain a paraffin oil with less than 10 percent by weight of aromatic components can, preferably a saturated, synthetic, branched paraffin oil used. This is preserved by mixing a fully hydrogenated liquid isobutylene polymer with any one high degree of geminal dimethyl branching (um

to generate a strong NMR band at about 8.58 τ) with a branched synthetic paraffin oil low degree of geminal dimethyl branching (indicated by a weak NMR band at about 8.58 τ) and with a high proportion of methylene groups not influenced by neighboring groups (es a strong NMR band is generated at about 8.84 to 8.85 τ). An example of such an oil is Oil J in Table III, showing a viscosity-temperature function VI of 83 and an average traction coefficient of 0.044 (at 304.8 m / min) shows. This branched paraffin oil preferably has the 10 to 90 percent by weight of paraffins with a high proportion of methylene groups influenced by neighboring groups and 10 to 90% paraffins with a low

Contains proportion of methylene groups influenced by neighboring groups, an average molecular weight in Range from 170 to 1000. This blended, synthetic paraffin oil can also be beneficial with

1 to 10 parts by weight, based on the mixture of branched paraffins, at least one other branched paraffin which corresponds to _{a fully hydrogenated polymer, copolymer or terpolymer of C 3} to C _{8 olefins.} Preferred branched paraffins in these mixtures correspond to fully hydrogenated polymers of propylene, 3-methylbutene-l, 4-methylpentene-l, 2,3-dimethylbutene-1, 1-hexene or 1-octene or a copolymer of propylene and ethylene. Also suitable as the transfer fluid is a hydrocarbon base which is a mixture of at least two branched paraffin oils, preferably a mixture of at least one branched paraffin oil with a strong band at 8.58 τ in the NMR spectrum with another branched paraffin oil that has a strong NMR band in the range from 8.84 to 8.85 τ, and 5 to 75% of a C ₁₃ - to C ₄₀ naphthene with a glass transition temperature of -90 to -30 ⁰ C contains. This naphthene has as its core structure a cyclohexylhydrindane, di (cyclohexyl) alkane, spirodecane, spiropentane, perhydrofluorene, perhydrobiphenyl, perhydroterphenyl, decalin, norbornane, perhydroindacene, perhydrohomotetraphthene, perhydroacenaphthene, perhydrophenanthene -, Perhydroindane - 1 - spirocyclohexane, perhydrocarylophyllene, pinane, camphane, perhydrophenylnaphthalene, perhydropyrene or adamantane radical.

In another embodiment of the invention, a lubricant and transmission agent is used in a power transmission system with friction drive which contains a hydrocarbon base with a kinematic viscosity at 98.89 ° C. in the range from 1.5 to 200 OcSt. According to the invention, this hydrocarbon base contains at least one saturated Q ₂ - to C ^ -adamantane compound which does not contain any elements other than carbon, hydrogen, fluorine or oxygen. If oxygen is present in these adamantane compounds, it must be in the form of an ether or ester group.

The saturated adamantanes preferred according to the invention are the following compounds:

(1) alkoxy derivatives of alkyl adarnantane (e.g. methoxy derivatives);

(2) perhydrogenation products of benzoxyadamantanes,

(3) diesters with 1 or 2 adamantane cores,

(4) Alkyl derivatives of the compounds mentioned, their Alkyl radical contains 1 to 10 carbon atoms,

(5) Cycloalkyl derivatives of the compounds already mentioned, the cycloalkyl radical being a cyclopentyl, Cyclohexyl or a mono- or dimethyl-substituted cyclopentyl or cyclohexyl radical contain,

(6) a Djcycloalkylderivat of Adamantanen, which as a dicycloalkylgruppe a Djcyplohexyl-, Di * contains (cyclohexyl) propyl radical or a mono-, di- or tetramethyl derivative of one of these radicals,

(7) an alkyl derivative of adamantane in which the Alkyl group preferably contains 1 to 10 carbon atoms,

(8) with both alkyl and cycloalkyl radicals substituted adamantane, the alkyl radicals containing 1 to 10 carbon atoms and as Cycloalkyl radicals Cyclopentyl, cyclohexyl radicals or their alkyl derivatives are present,

(9) Fluorine substitution products of the enumerated saturated adamantane compounds.

Examples of the present invention preferred saturated adamantane compounds are perhydro-1-benzoxyadamantan obtained at by Perhydrieren of 1-Benzoxyadamantan in the presence of a Raney nickel catalyst at 200 ⁰ C under a hydrogen pressure of 211, and the Monoester of 1 -Adamantancarbonsäure.

The following diesters are particularly valuable for the purposes of the invention:

I. Diesters of alkyl-substituted 1,3-adamantane-diols with alkanecarboxylic acids or cycloalkanecarboxylic acids.

II. Diesters of alkyl-substituted monohydroxyadamantanes with alkanedicarboxylic acids or cycloalkanedicarboxylic acids.

Compounds obtained by alkylating adamantane hydrocarbons in the C ₁₀ to C ₃₀ range with one to four free bridgehead positions are also suitable.

Fluorine and perfluoro derivatives of any of the adamantane compounds listed, as obtained by passing the adamantane compounds in the vapor phase over a CoF ₃ -BeU in a tubular reactor kept at about 350 ° C., are also very suitable as transfer liquids.

Particularly preferred adamantane compounds are dimethylbutyladamantane, dimethyloctyladamantane, Dimethylcyclopentyladamantane, dimethylcyclohexyladamantane, dicyclohexylethyladamantane, Dimethyladamantanedipelargonate and dimethyladamantanedicaproate, in which all substituents of the adamantane are bound in bridgehead positions.

Another preferred embodiment of the invention relates to a hydrocarbon base which is suitable as a transfer fluid and which contains a mixture of substituted adamantanes. These substituted adamantanes were preferably obtained by reacting a petroleum hydrocarbon stream which is essentially free of aromatic or olefinic unsaturated compounds and which contains at least one perhydrogenated aromatic hydrocarbon with three rings and at least ^ carbon atoms in a temperature range from -5 to +5 ⁰ C on an aluminum halide analyzer, The starting hydrocarbons are kept in contact with the aluminum halide catalyst until at least a substantial part of the perhydroaromatic compound has been converted into a hydrocarbon with an adamantane structure. The adamantanes obtained in this way can be modified further by alkylation.

A preferred blended transfer liquid contains perhydrophenanthrene and 0.1 to 10 parts Cyclopentyldirnethyladamantane per part perhydrophenanthrene.

Example I shows the production of an α-methylstyrene polymer. one of them raised a proportion of 1,3,3-trimetnyM'phenylindan and a smaller proportion of trimers and of unsaturated α-methylstyrene dimers contains,

Example II shows the hydrogenation of poly (α-methylstyrene) oil from Example I with the formation of a carbon

hydrogen base, which is about 70% 1,1,3- '
contains hexylhydrindane.

Example III illustrates the production of a highly branched paraffin oil with a good traction coefficient and good viscosity index by hydrogenating an oil obtained by thermal cracking of high molecular weight polyisobutylene was obtained.

Example IV shows the preparation of a branched paraffin oil by hydrogenating poly-1,3- (3-methylbutene-1).

Example V shows the preparation of a branched paraffin oil by hydrogenating a liquid polymer of 2,3-dimethylbutene-l.

Example VI illustrates the beneficial behavior of two transfer fluids according to the invention in a traction drive compared with a conventional naphthenic lubricating oil (oil 35) and a polybutene oil obtained by polymerizing a butylene mixture (oil 23).

Example I.

466 g of a commercially available -methylstyrene polymer, which was obtained by conventional acid-catalyzed polymerization, are placed in a 1-1 round bottom flask equipped with a 2.54 cm column. The polymer is distilled at a pot temperature of about 290 "C and a temperature of the vapor phase of about 210 ⁰ C under a vacuum of about 6 mm mercury substantially without reflux and without fractionation. This gives 373 g of distillate and about 73 of a g after The commercially available methylstyrene polymer has a softening point of 98.89 ° C., a Gardner-Holdt viscosity of JL, a specific gravity of 1.075, a refractive index at 20 ° C. of 1.61, a molecular weight of 685, the iodine number 0, the acid number 0 and the saponification number 0.

Example II

300 g of the distillate obtained in Example I are placed together with 7.5 g of a Raney nickel catalyst in an autoclave made of corrosion-resistant steel and 210.9 atmospheres of pure hydrogen pressure are applied while heating is carried out until the temperature in the autoclave is 150 ' C is reached. At this moment an exothermic reaction occurs and the heating is interrupted. The temperature is allowed to rise to about 220 ⁰ C and hold for another 6 hours a hydrogen pressure of 210.9 atm upright. The autoclave is then slowly cooled to room temperature, the hydrogen pressure being maintained at 210.9 atmospheres in order to avoid dehydrogenation of the hydrogenated product. The perhydrogenated poly ((i-methylstyrene) oil obtained is fractionated in order to remove constituents boiling below 125 ° C. The properties of the perhydrogenated product obtained are listed in Table II under oil 5. The traction coefficient of this liquid is measured in a device according to FG R o u η ds, Journal of C & E Data, .5, pp 499 to 507 (1960), using two steel pressure ball bearings on 170 ml of the lubricant as a function of load, speed and oil temperature.

The coefficient calculated from these measurements is shown in Table II. The transmission fluid is also used as a lubricant in an experimental transmission with a built-in dynamometer

ifr

Speeds from 609 to 914 m / min and tested in an automobile with a speed converter. The behavior in these tests shows that the oil is a satisfactory transfer fluid Has properties, but the low temperature properties of the oil for use in automobiles not enough. Nuclear magnetic resonance analysis shows that this oil is this example about 20% trimers (predominantly hydrindane), about ίο 10% 2,5- (dicyclohexyl) -2-methylpentane and about 70% 1,1, .l-TrimethyW-cyclohexylhydrindane contains.

Example III

A commercially available polyisobutylene polymer with a molecular weight of 10,000, which was produced by low-temperature polymerization using an AlCl ₃ catalyst, is thermally cracked according to Example I. About 50% of the polymer breaks down to isobutylene. The remaining portion is hydrogenated with the aid of a catalyst containing 0.5% palladium on activated carbon at 275 ° C. and a hydrogen pressure of 105.5 at for 8 hours. The hydrogenated polyisobutylene obtained! has the properties listed in Table II Door Oil 34 and shows a strong NMR band at 8.58 τ and almost no NMR band at 8.84 to 8.85 τ.

Example IV

A dry WI lemonade bottle is charged with 235 g of dry, pure 3-methylbutene-1. 16 ml of a 1 molar solution of Al ₂ (CH ₂ CHO ₃ Cl., In cyclohexane and 14 ml of a 1 molar solution of TiCl ₄ in hexane. The reaction takes place at 30 ^° C. for a period of 20 hours.

The mixture is then ^{stirred for 1} Z ₂ hours with 5 ml of concentrated ammonium hydroxide and the catalyst residue is filtered off from the mixture. The solvent is removed from the product by distillation and distilling the remaining solvent-free oil at about 0.5 mm Hg to remove lower than 150 ⁰ C boiling products. 104 g of an oily distillation residue with a kinematic viscosity at 98.89 × of 175 cSl are obtained. Nuclear magnetic resonance analysis showed that the structure

of the polymer units by 1.39 addition and not comes about by the expected 1,2 addition. The product obtained therefore corresponds to poly-1.3- (3-methylbutene-1). The product obtained is as described in Example III. cracked and hydrogenated

and the resulting oil is fractionated. One of the Fractions of this oil are shown in Table 11 as oil 31. It is also possible to use poly-2-methylbutene-1, which is obtained according to Hydrogenation is a valuable part of the door of a power transmission wedge is.

B e i s ρ i e 1 V

2,3-Dimethylbutene-1 is reacted over a catalyst at 30 ° C. for 20 hours as in Example IV, which consists of 1.17 mol of ethylaluminum scsquichlo-

rid and 1 mole of titanium tetrachloride was prepared. After removing the unreacted monomer distillation from the catalyst-free reaction mixture gives an oil in 72% yield. This oil is hydrogenated as in Example III. The properties

Shafts of the hydrogenated oil are shown in Table 11 under Oil 9.

The liquid polymers of 2,3-dimethylbutene-1

are due to their thermal stability and the stability against oxidation, as they are from the for oil 9

Properties listed in Table II can be seen, of great value as transmission fluids or as components of transferred liquids. Polymers with a higher molecular weight can be obtained from 2,3-dimethylbutene-1 using a cat ionic system, for example a Bf-y catalyst, at low temperature (such as -78 "C). For example, with BF, at -78 "C in I3.5% yield, based on the olefin used, a high molecular weight 2,3-dimethylbutene-1 polymer, which is optically transparent and hard and has a high molecular weight (low viscosity 0.1 to 30 "C in cyclohexane), these high polymers are useful additives for wax or ParalTingcmisclie to this increased hardness and To give strength.

Example VI

The oil (oil 5) from Example I is tested in a traction drive. The oils I, 23 and 35 from Tables 1 and H are tested in the same way in this transmission. A comparison of the maximum torque that can be obtained without slippage in this power train with each of these four fluids is shown along with the viscosity index and that in the laboratory tester at 35 153 kg / cm ² , 93.33 ° C and 304.8 m / min traction coefficients obtained are shown in Table V. It can be seen from this that oil 1 has the best combination of traction and flow properties (e.g. viscosity index), oil 1 only has a traction coefficient of 9% greater than oil 23 in the laboratory device and yet withstands a 32% higher torque without Slip as oil 23. It can also be seen that oil 5, which contains about 20% perhydrogenated (i-methylstyrene trimers, has the best traction properties but the lowest viscosity index of all four oils.

Table I.

Structure and / or method of manufacture

40

45

50% oil 6 + 50% oil 34 - days (freezing temperature) = -93 ° C

oil 1 + 4% polyacrylate-based VJ improver + 35 ppm parts per million parts silicon-containing antifoam

5% oil 40 + 95% oil 6

30% oil 6 + 70% oil 34 - day = - 88.5 ° C Perhydrogenated methyl styrene dimers (PHAMSD), 10% DCHMP, 20% trimers (predominantly hydrindane), 70% DMMCHH

60

65

Structure and / or method of manufacture

DCHMP

Tg. = -66 "C, density = 0.93 oil corresponding to oil 5, but with 15% trimers
Perhydration of poly (4-methylpentene-1)

H
-C-

-C-H

A it 14 ί ^Λ 1-1

I I

H ₃ CC-CH ₃ H ₃ CC-CH ₃

H H

Day = -86 ° C

10% Oil 6 + 90% oil 19 - Tg = -95 C ^Ü Perhydrogenated polymer of (2,3-Dimethylbulen-1).

CH ₃

CH ₃

-C-H

H
-C-

1 ^H.

H ₃ CC CH ₃ H ₃ CC CH ₃

H H

Tg. = -74 ⁰ C

50% oil 6 + 50% oil 19 days = -81 ° C 50% tetraisopropyldecalin (TIPD) + 50% oil 19 days. = -78 ° C
50% oil 22 + 50% oil 34
50% oil 6 + 50% oil 19 - Tg. = -83 ° C Perhydrogenated u-methylstyrene dimerisate - Tg. = -56 ° C (30% DMMCHH, 30% DCHMP, 40% trimers and small amounts of tetramers)

Perhydrogenated styrene dimer (PHSD) - avg. Molecular weight 305 (15% hydrindane dimer and dicycloalkane dimers, 85% trimers with a small amount of tetramers) - boiling range 150 to 235 ° C / 0.1 mm Hg

CH ₃

CH ₃

I Ή Η C — C — C HHH

Dicycloalkane

Hydrindane
Day = -54 ° C

20? 525/496

continuation

Structure and / or method of manufacture

oil 6 + y ₂ % 4,4'-tetramethyldiaminophcnylmclhun (antioxidant) -I- ¹ U ¹ Yn N - phenyl -1 - naphthalumin + 1% tricresyl phosphate (antiwear agent)

Tetraisopropyldecalin (TlPD)

JC ₃ H ₇

C ₂ H ₅

H H

CH,

CH ₃

CH ₃ CH ₃

H H

IO

1-C ₁ H ₇

C ₃ H ₇

Day = -48.3 ° C

50% oil 22 + 50% oil 19

Strong hydrogenation of oil 23 (polybutene A)

30th

35

40

45

Iodine number = 0.1
Day = -93 ° C

70% oil 34 + 30% hydrogenated styrene trimer oil (15.9 cSt at 98.89 ° C)
(Freezing temperature (Tg.) Of the mixture
= - 102 ° C) with less than 10% of tetramers and dimers

30% oil 17 + 70% oil 34 - days. = -88 ° C

Naphthene distillate hydrogenated under severe conditions (obtained by further hydrogenation of oil 27)

Fractions of acid-polymerized mixed fractions mixed by "dumbbell blending" Butenes which were then subjected to mild hydrogenation (as in U.S. Patent 3,100,808). The received oil has a flash point of 143.3 ° C, a boiling range from 243.3 to 560 ° C (90%), has about 40% geminal configuration and has less than 5% cyclic residues - Tg. = -88 ° C, middle Molecular weight: 375

15% of an oil with an ASTM-VI (D 2270) of - 508 and a kinematic viscosity KV of 34.75 cSt at 98.89 ° C by hydrogenating a u-methylstyrene polymer + 84% of an oil with an ASTM-VI of 27, obtained by strong hydrogenation (to less than 1% aromatic content) one Naphthene distillate with 110 SUS (at 37.8 ° C)

Fraction with a narrow boiling range (215 to 285 ° C / O, 2 mm Hg, average molecular weight 496) of oil 43 - Tg. = -84 ° C

55

25th

Structure and / or manufacturing url

Perhydration of ö! 40 to "Hydimer" oil with 55% dimers with hydrindane and di (cycloalkane) structure and 45% trimers. Mean molecular weight at 147; Boiling range 150 to 196 ° C / 0.3 mm Hg. Structures of the dimeric portion of the oil

Day = -75 ° C

Further hydrogenation of oil and removal of remaining aromatics by adsorption on silica gel

30% oil 34 + 70% of an oil with a viscosity of 2.94 cSt (at 210 ° C) corresponding to oil 26, but with 40% trimers - Tg. = -85 "C 50% oil 34 + 50% of a hydrogenated polystyrene oil with 8 cSt (at 210 ° C) corresponding to oil 15 with a content of 80% trimers (some tetramers) and 20% dimers - Tg. = -94 ° C

Hydrogenation of oil 35 to C _A = 2% (catalyst sulfided Ni / Mo oxide, 0.5 LHSV, freshly added / 3.5 LHSV from the circuit, 343.3 ° C, 70.3 at H ₂ ), iodine number 15.3 - Tg = -79 ⁰ C.

Hydrogenation of polymerized 3-methylbutene-1

CH ₃
-C -

H
-C-

H
-C-

CH,

195 UVA = 2.5
Day = -87 ° C

1,3- (5,7-dimethyl) adamantyl dipelargonate
(DMAP) ₀

CH ₃ -

O
-QC- (CH ₂ I ₇ -CH ₃

Day = -87 ° C

continuation

Structure and / or method of manufacture

Hydrogenation of an extract of furl'uralextruktion of a naphthene distillate containing 90% gel-like aromas with 150 SUS up to a content of 30% gel-like aromatics —Tg. = -63.5 "C hydrogenation of cracked polyisobutylene. The hydrogenated oil obtained has a strong NMR band at 8.58 τ and no noticeable band at 8.84 to 8.85 τ. Initial boiling point = 343.3 ° C., 90 % share at 532 ^° C

CH ₃
-C—

-C-H

CH ₃

H
C-

CH ₃

H
-C-

195 UVA = 1.88 - day = -67 ° C

Further hydrogenation of oil 37; 195 UVA

= 0.00 days = -64 ⁰ C
Hydrogenation of Poly (I-Hexen)

H
-C-

H
C-

H
-C-

-C-H

H -C-

-C-H

CH ₁

C ₂ H ₅

to

195 moles UVA = 0.77; average weight = 409 - day = - Π 2 ° C

ASTM-Ö1 No. 3 (naphthenic lubricating oil), iodine number 25.1, 43% gel-like aromatics, 21% C _A - Tg. = -77 ° C

Hydrogenation (0.5 LHSV, freshly added, 3.5 circuit - LHSV, 343.3 ° C, 70.3 at H ₂ , Ni-Mo) with 300 SUS at 37.8 ° C naphthen distillate, obtained by the method according to U.S. Patent 3,184,396 Hydrogenated Polypropylene - Narrow Fraction of Oil 45 (195 to 260 ° C / 0.2 mm Hg)

35

45

I.
C ₄ H ₉

195 UVA = 0.36

Acid-polymerized styrene, 55% dimers and 45% trimers - Tg. = -48 ° C Hydrogenation of the copolymer of 51 moles of propylene and 49 moles of butene-1

55

6o

oil

195 UVA = 0.12 days. = -83 ° C

Structure and / or leaning belt

40% oil 26 + 60% oil 38 - day = ~ 80 "C
Boiling range 152 to 3OO ° C / Q, 2 mm Hg; Hydrogenated polymer (Ziegler catalyst) of butene-1

H
C-

C ₂ H ₅

-C-

195UVA = 0.17; Tg = -82 ⁰ C mittlercsMolgewicht557-.

Hydrogenated copolymer (per U.S. Patent 2,327,705) at 56 mole percent Ethylene and 44% propylene. 195 UVA = 0.00 days. = -96 ° C

Hydrogenated propylene polymer (further boiling ' Area)

H
-C-

-C-

CH,

195 UVA = 0.98 days. = -79 ° C

Hydrogenated octene polymer

Hydrogenation of a commercially available polybutylene with an iodine number of 48; kinematic Viscosity (98.89 ° C = 3.25) (the oil cracked slightly during the hydrogenation)

Hydrogenated polymer of pentene-1 -
Day = -106 ° C

50% oil 6 + 50% oil 22

A naphthen distillate (55 SUS at 37.8 ° C) with a content of 40% gel-like aromatics was hydrogenated under severe conditions to a content of less than 0.4% aromatics. The remaining aromatics were then removed by adsorption on silica gel. An oil was obtained with a UVA 260 of 0.00.

50% oil 50 + 50% oil 6

oil 36 + 0.5% N-phenyl-1-naphthylamine, 0.5% 4,4'-tetramethyldiaminodiphenylmethane, 1% tricresyl phosphate (to increase the traction coefficient)

Hydrogenated Dimerenöl (boiling range 195-250 ° C / 1 mm Hg) obtained by distillation of the reaction product from the '/ 2-hour reaction at 125 ⁰ C of catalytic gas oil (boiling range 218.3 to 329.4 ° C) with formaldehyde (1 mol Formaldehyde per 2 moles of aromatics) in the presence of an amount by weight corresponding to the formaldehyde of a catalyst consisting of 3 moles of acetic acid and 1 mole of sulfuric acid.

Tabillull

21 092 28 123 Truklinnsknefli / ien 28 123 ι 35 153 I «2.9
m / min KV Viscosilillslitdex VTF (Ιι. ,, Ι, 93.3 37.8 U>, 48 m / mii V
148.9 93.3 57 MOCK
punkl πι 0.033 0.056 0.044 0.049 28 123 98.89 "C ASTM 111 0.029 0.055 kg / cm ' 0.045 0.049 93.3 6.69 62 12th "C 0.027 0.059 28 123 0.050 0.050 0.059 9.09 122 54 -37.2 I. 0.030 0.059 93.3 0.049 (0.055) 0.058 4.28 -45 -9 -37.2 2 0.030 0.052 0.055 0.048 0.049 0.057 4.50 41 10 -23.3 3 0.026 0.059 0.054 0.049 0.045 0.059 5.50 -46 37 -37.2 4th 0.024 0.054 0.054 0.040 0.041 0.056 4.49 -42 60 -20.6 5 0.024 0.053 0.0535 0.048 0.047 0.055 4.80 19th 2 -20.6 6th 0.029 0.052 0.053 0.046 (0.053) 0.055 4.29 48.5 48 -45.6 7th 0.025 0.054 0.053 0.041 0.048 0.056 7.98 -16 -20 -34.4 8th 0.027 0.052 0.052 0.052 0.048 0.056 4.40 28 72 -12.2 9 0.033 0.050 0.052 0.046 (0.054) 0.055 4.93 -88 46 -45.6 10 0.019 0.051 0.051 0.046 (0.055) 0.054 4.95 76 -38 11th 0-026 0.054 0.051 0.044 0.050 0.056 4.55 28 -43 -43 12th 0.034 0.053 0.050 0.047 0.052 0.056 8.02 -100 89.5 -34.4 13th 0.028 0.052 0.050 0.042 0.047 0.058 8.21 -141 -150 -9.4 14th 0.024 0.049 0.050 0.040 0.044 0.049 9.30 00 52 -15 15th 0.021 0.050 0.050 0.041 0.043 0.054 6.54 -465 68 -20.5 16 0.027 0.050 0.049 0.041 0.042 0.052 4.32 36 58 -12.2 17th 0.022 0.049 0.049 0.041 0.048 0.052 5.20 74 22nd -34.4 18th 0.021 0.047 0.048 0.046 . 0.045 0.053 5.17 61 40 -45.6 19th 0.026 0.047 0.048 0.043 0.047 0.056 4.62 -15 66 -34.4 20th 0.021 0.048 0.047 0.039 0.044 0.048 4.31 24 41 21 0.025 0.049 0.046 0.037 0.043 0.050 4.92 53 63 -48.3 22nd 0.022 0.044 0.045 0.035 0.039 0.050 4.32 12th 22nd -51 23 0.021 0.048 0.045 0.039 0.047 0.051 7.29 69 45 -31.7 24 0.022 0.051 0.045 0.037 0.043 0.045 3.30 -18 54 -37.2 25th 0.020 0.048 0.045 0.037 0.047 0.052 4.56 26th 52 -34.4 26th 0.021 0.050 0.044 0.038 0.048 0.048 4.38 40 50 -40 27 0.019 0.046 0.043 0.037 0.042 0.050 5.27 52 36 -34.4 28 0.021 0.047 0.043 0.039 0.046 0.050 4.66 22nd 85 -34.4 29 0.023 0.044 0.043 0.035 0.041 0.045 5.47 31 -20 -37.2 30th 0.019 0.041 0.043 0.035 0.038 0.045 7.0 95 98 -31.7 31 0.018 0.047 0.042 0.033 0.043 0.044 5.13 -77 26th -56.7 32 0.016 0.040 0.041 0.035 0.042 0.044 8.12 106 10 -23.3 33 0.010 0.038 0.041 0.027 0.038 0.044 4.41 -11 60 ; -5ΐ 34 0.010 0.039 0.041 0.031 0.040 0.042 4.64 2 64 -34.4 35 0.017 0.042 0.040 0.030 0.036 0.039 5.68 67 101 -31.7 36 0.12 0.034 0.037 0.029 0.033 0.039 9.27 71 -86 -34.4 37 0.002 0.037 0.036 0.029 0.037 0.039 7.40 110 73 -3 ', 7 38 0.008 0.034 0.035 0.031 0.037 0.036 5.32 -241 38 -56.7 39 - 0.038 0.035 0.029 0.039 0.034 6.18 82 65 -9.4 40 0.004 0.036 0.034 0.029 0.036 0.036 4.24 12th 131 -31.7 41 0.014 0.037 0.032 0.026 0.026 0.037 10.38 71 78 - 42 0.010 0.041 0.032 0.023 0.033 0.033 8.50 153 «150 - 43 0.009 0.032 0.031 0.023 0.029 0.035 4.49 80 86 26.1 44 0.038 0.046 0.031 0.037 0.048 0.031 «140 93 -28.9 45 0.030 0.032 0.030 2.84 78 33 <-45.6 46 0.024 0.051 0.029 0.040 0.046 3.67 93 -51 47 0.024 4.38 1 48 0.045 49 0.048

2 «)

UVA

0.003 0.003

0.022 0.003

0.055

0.024

0.022

0.003

0.02

0.003

0.01

0.027

0.000

0.31

0.001

0.01

0.027

0.000

0.027

0.027

0.054

0.5

1.0

0.07

0.5 0.05 0
0.01

0.01

0.13

0.015

0.06

ΠΙ me

use

% Rise

-2.3

54.7 0 10.8 0 51.1 0.22 1.6 0.23 - 0 2.1 0.6 5.8 1.0 2.5 0 1.0 0.6 -1.0 0 -2.2 0 2.8 0.4 9.5 0 2.4 1.85 15.5 0 4.6 0.6 2.7 0.12 -0.9 0.1 0.8 20.6 2.8 6.9 0.1 3.1 0.1 9.6 0.1 4.2 0.1

39

continuation

21092 28 123 Traction coefficients 28123 t 35 153 182.9
m / min KV Viscosity index VTF btoc k- 260 Dl after TAN 93.3 37.8 0.48 m / min C.
148.9 93.3 61 Point use ΠΙ 0.021 0.050 0.043 0.044 28 123 98.89 ⁰ C ASTM 48 ° c UVA % Rise * J1 0.021 0.053 kg / cm ' 0.048 0.047 93.3 2.24 55 10 ^ v ₃₇₈ 0.12 0.013 0.043 28 123
° 0.027 0.038 2.87 31 6th 0 50 0.024 0.045 93.3 0.039 0.045 4.64 2 -31.7 51 0.050 6.27 -38 + 1.7 -0.4 52 0.053 -0.4 53 0.037 0.043

Table III

Dl Average
> action coefficient DMAP VTF-VI KV KV floor
Point Day composition 304.8 m / min *) % **) 98.89 ° C 37.78 ⁰ C ° C ⁰ C A. 0.051 38 50 7.6 76.7 -31.7 -105 70% oil 34 + 30% hydrin dan trimers of a-methyl- styrene B. 0.050 35 -46 4.3 44.5 -12.2 -57 Perhydro-ortho-terphenyl C. 0.049 32 -36 4.2 40.5 -59 ^ i tin;
Perhydro-ortho-terphenyl (contaminated - contains some other perhydro terphenyle) D. 0.047 27 49 4.4 29.6 -28.9 -89 70% oil 34 + 30% oil F. E. 0.047 27 77 4.2 23.8 -105 70% oil 34 + 30% oil B. F. 0.046 24 10 4.5 37.4 -20.6 -68 Perhydrogenated dimerizate of Methyl styrene, 15% tri- mere, average molecular weight 251 G 0.045 22nd -66 5.7 90.3 -20.6 -66 30% oil S + 70% TIPD (oil 17) H 0.044 19th 38 4.7 34.6 -86 1,3- (5,7-dimethyl) adamantyl- dicaproat (DMAC) (density 1.009) I. 0.044 19th 42 4.0 22.5 -45.6 -89 50% oil F / 50% strong hy third solvent-based Purifies lubricating oil (215 aniline number, 1.472 Refractive Index, 40.6 SUS at ⁰ C 98.89, 114.1 SUS at 37.78 ° C) J 0.044 19th 83 4.3 24.6 -31.7 -112 50% 0134 + 50% oil S. K 0.043 16 70 5.6 40.0 -42.8 -106 50% oil 34+ 50% oil G. L. 0.043 16 23 4.1 29.1 -79 50% oil S + 50% oil B M. 0.042 14th 56 4.3 27.6 -89 90% oil S + 10% oil B N 0.042 14th 58 3.5 19.0 -37.2 -90 55% oil F + 45% commercial common polybutene oil O 0.042 14th 79 4.0 21.8 -95 Equal parts by weight of oil F, oil S and oil 46 P. 0.040 8th 43 4.2 27.6 -87 70% oil S + 30% oil B. η 0.040 8th 60 4.4 28.2 -95 90% oil S + 10% perhydrated tes p-terphenyl R. 0.040 8th -64 5.6 84.0 -17.8 -54 Perhydrogenated 9-benzylidene fluorene

* \ Arithmetic mean of the traction coefficient at 304.8 m / min (speed of rolling contact and 21092 kg / cm ⁱ / 93.3 ° C;

^ BKci 28123kg / cm793.3 ° C; 28123 kg / cm ^J / 148.9 ° C and 35153 kg / cmV93.3 ° C. ♦ *)% increase or decrease in the average traction co-efficient compared to that of DMAP (CJl W).

2372

continuation

Average DMAP VTF-VI KV KV floor Day composition oil fraction coefficient % * ♦) 98.89 ° C 37.78 ° C Point ⁰ C 304.8 m / min *) 5 64 4.6 29.6 ° C -96 oil equivalent to oil 19 S. 0.039 5 42 5.4 44.8 -88 50% oil S + 50% oil G T 0.039 3 107 1.7 5.2 -119 Cyclopentyl dimethyl U 0.038 adamantan 3 105 4.1 20.3 -122 75% oil 34 + 25% oil V 0.038 0 80 7.0 55.5 -89 DMAP (see oil 32, table II) W. 0.037 -5 92 4.0 20.7 -56.7 -107 50% oil S + 50% oil 46 X 0.035 _5 83 3.9 20.9 -97 50% oil F + 50% oil 46 Y 0.035 -5 133 1.7 5.0 -101 Perhydrophenanthrene Z 0.035 -5 50 4.3 28.2 -57 90% oil S + 10% oil 17 / VA 0.035 -40 (TIPD) -8th 26th 4.4 33.4 -77 oil 35 (ASTM oil 3) AWAY 0.034 -16 110 1.55 4.42 -37.2 -52 Ethyl adamantane, b.p. 224 ° C AC 0.031 -22 62 1.16 2.89 -26 Dimethyladamantane, AD 0.029 . Kp. 204 ° C, mp -26 ⁰ C.

*) Arithmetic mean of the traction coefficients at 304.8 m / min (speed of the rolling contact and 21092 kg / cm ² / 93.3 ° C;

28123 kg / cm737.8 ° C; 28123 kg / cm ² / 93.3'C; 28 123 kg / cm ² / 148.9 ° C and 35 153 kg / cm ² / 93.3 ° C.
**)% increase or decrease in the average traction coefficient compared to that of DMAP (oil W).

Unless otherwise specified, all percentages are percentages by volume; however, as the densities of most If the oil components of the blends mentioned are close together (T 10%), the percentages by volume are the Details in percent by weight are about the same.

Table IV

(Naphtha lubricating oil) λ CTy \ f! More experimental Highest, without ptl (Polymer from butene mixture) Aj I IVl-V I Traklionskocffizienl Slippage possible Ul (Naphthene-paraffin mixture) Torque (Hydrogenated methyl styrene dimer) -11 0.042 mkg . 35 53 0.044 12.9 23 62 0.0485 14.2 1 -46 0.049 18.8 5 19.9

Oil 1 shows a behavior in the traction drive which is satisfactory for automotive use.

The properties of oil A according to Table IH make it clear, however, that with this oil in comparison to every other oil shown in the table a power transmission at higher torques without slippage can be operated.

2372

Claims (4)

Hydrogen atom, methyl, ethyl or isopropyl resol, 5. CJbertragungsnUssigkeit according to claims 1 to 4, characterized in that it contains a hydrocarbon base which boils predominantly above 260 "C, shows a UV absorption below 0.5 at 260 ηΐμ and as perhydrogenated polymer g) contains at least 10 percent by weight of a C1 (1 to C22 hydrindane of the general formula in which R1 'is a methyl or ethyl radical and R2, R3, R4, R ^, r ;, r ;, R ^ and R ^ Hydrogen atoms or methyl radicals. 6. Transfer liquid according to claims 1 to 5, characterized in that it contains as a liquid, synthetic olefin polymer i) the polymerized radicals of at least one of the olefins isobutylene, 3-methylbutene -1,4-methylpentene -1 or 2 , 3-dimethylbutene-1. 7. Transfer fluid according to Claims 1 to 6, characterized in that it contains a hydrocarbon base with at least 5% of a perhydrogenated trimer or co-primer of a styrene d) elder 8. Transfer fluid according to claim 7, characterized in that it contains a hydrocarbon base with at least 5% of a perhydrogenated trimer or co-trimer which contains 25 to 100% of a C24- to C32-hydrindane of the general formula R «CC R7 R9 R3 11 Claims 1 to 10, characterized in that it contains a highly hydro-refined naphthenic lubricating oil I ") with more than 50% naphthenically bonded carbon atoms, which has a viscosity in the range from 30 to 10,000 SUS and a UV absorption of less than 0.05 260 ιημ shows 12. Uberlragungsfiüssigkeit according to claims 1 to 11, characterized in that it contains a hydrocarbon base, the naphthene g) perhydro-o-terphenyl, perhydric 9-benzylidene fluorene or a mono-, di-, tri or tetramethyl derivative contains one of these compounds, the UV absorption being less than 0.1 at 260 μm. 13. Transmission fluid according to claims I. to 12, characterized in that it contains a hydrocarbon base with an initial traction coefficient which is greater than that of 1,3- (5.7-dimethyl) adamantyl dipelargonate measured at 182.9 m / min per 28.123 kg / cm2 . contains, wherein R1 to R9 are hydrogen atoms, methyl, ethyl and isopropyl radicals. 9. Transfer fluid according to Claims 1 to 8, characterized in that it contains a tetraalkyl-substituted decalin as substituted C12 to C30 decalin e). 10. Transfer fluid: according to claims 1 to 9, characterized in that it contains a hydrocarbon base with more than 5% of the substituted C12- to C30-decalin e) and less than 1% of gel-forming aromatics, based on the decalin, the UV absorption 0.1 at 260 ΐημ shows. The invention relates generally to the use of certain naphthenes and branched paraffins as power transmission fluids. It further includes certain novel transfer fluids having good low temperature properties which contain a mixture of at least one branched high viscosity index paraffin and at least one low viscosity index high traction coefficient naphthene. The mixture of the paraffin and the naphthene preferably has an average molecular weight in the range from 170 to 1000, in particular 220 to 375. Paraffins with a high degree of geminal branching and a glass transition temperature in the range from -120 to -50 ° C. are particularly preferred Naphthenes with a freezing temperature in the range from -90 to The invention is a transmission fluid for power transmission systems based on hydrocarbons with a kinematic viscosity of 1.5 to 200 cSt at 98.89 ° C, consisting of a) a paraffin oil with less than 1 percent by weight of gel-forming aromatic hydrocarbons; b) a mixture of 1. 10 to 90 percent by weight of at least one branched paraffin oil which has a strong band at 8.58 τ and at most a weak band in the range from 8.84 to 8.85 τ in the nuclear magnetic resonance spectrum, and 2. 10 to 90 percent by weight of at least one branched paraffin used in nuclear magnetic Resonance spectrum a strong band in the range from 8.84 to 8.85 τ and at most has a weak band in the region of 8.58 τ; R ₃ , IO Patent claims: 1, power transmission fluid based on hydrocarbons with a kinematic Viscosity from 1.5 to 20OcSt at 98.89 "C, consisting out a) a paraffin oil with less than 1 percent by weight of gel-forming aromatic hydrocarbons; b) a mixture of 1. 10 to 90 percent by weight of at least one branched paraffin oil which has a strong band at 8.58 τ and at most a weak band in the range from 8.84 to 8.85 τ in the nuclear magnetic resonance spectrum, and 2. 10 to 90 percent by weight of at least one branched paraffin used in nuclear magnetic Resonance spectrum a strong band in the range from 8.84 to 8.85 τ and at most a weak band at 8.58; c) at least one branched paraffin, the repeating units of which are at least 33% the structure in which R _{1 is} a hydrogen atom or a methyl radical and R _{2 is} an isopropyl or isobutyl radical; d) a perhydrogenated polymer, copolymers or terpolymers of 40 1. styrene, 2. a-methylstyrene, 3. / i-methylstyrene or 4. a derivative of styrenes substituted by one or two methyl radicals on the ring I, 2 or 3; e) a substituted C ₁₂ - to C ₃₀ -Dekalin containing as substituents at least one of the radicals C ₁ - to Cs-alkyl, C ₅ - to C ₆ cycloalkyl, C ₆ to CjQ-alkylcyclohexyl or C ₆ - to C _{Contains 10} -alkylcyclopentyl; a highly hydro-refined naphthenic lubricating oil that is less than 1% gel-forming aromatic Contains hydrocarbons; g) a Cj ₃ to C ₄₀ naphthene with a perhydroterphenyl or perhydrofluorene radical as the basic structure; h) at least one C ₁₂ to C ₄₀ adamantane compound which contains no elements other than carbon, hydrogen, fluorine and oxygen and in which, in the presence of oxygen, it is in the form of an ether or ester bond; or off i) a mixture of at least one of the constituents a), d), e), f), g), h) with 0.1 to 20 parts by weight of at least one liquid, synthetic polymer, copolymer or terpolymer of a C ₃ - to CVOIellin and given fulls
k) usual additives. 2. UberlragungsllUssigkeit according to claim I, characterized in that the hydrocarbon-based Duss 5 to 75 weight percent of a C ₁ to C comprises _{r 4ü} -Naplühens with a glass transition temperature between -90 and -3O ⁰ C, which as a Grundslruktur Cyclohexylhydrindan-, di (cyclohexyl) alkane, spirodecane, spiropentane, perhydrofluorene, perhydrodiphenyl, perhydroterphenyl, decalin, norbornane, perhydroinidacene, perhydromonotetraphthene, perhydroacenaphthene, perhydrophenanthrene, perhydrochrysenic, perhydroindane - 1 - -, camphane, perhydrophenylnaphthalene, perhydropyrene or adamantane radicals. 3. Transmission fluid according to claims 1 or 2, characterized in that it as a saturated adamantane compound h) a compound from one of the following classes a) the alkoxy derivatives of alkyl adamantanes, b) the perhydrogenation products of phenoxyadamantanes, c) the diester with one or two adamantane cores, d) the alkyl derivatives of a), b) and c), in which the alkyl radicals have 1 to 10 carbon atoms, d) the cycloalkyl derivatives of a), b), c) and d), in which the cycloalkyl radical is a cyclopentyl, Is cyclohexyl or a mono- or diimethylcyclopentyl or cyclohexyl radical, 0 of the dicycloalkyladamantanes, in which the dicycloalkyl radical a dicyclohexyl, di (cyclohexyOpropyl- or a mono-, di-, tri- or Tetramethyl derivative is one of these radicals, g) the alkyl adamantanes, in particular with alkyl radicals with 1 to 10 carbon atoms, h) one substituted by alkyl and cycloalkyl radicals Adamantanes, in which 1 to 10 carbon atoms are alkyl radicals and as cycloalkyl radicals Cyclopentyl, cyclohexyl radicals or their alkyl derivatives are present, or i) the fluorine substitution products contain one of the adamantane compounds mentioned. 4. Ubertragungsflüssigkeit according to claims 1 to 3, characterized in that it contains a hydrocarbon base boiling predominantly above 260 ⁰ C, having a UV absorption below 0.5 at 260 ηΐμ and g as perhydrogenated polymer, copolymer or terpolymer) 5 to 50% of a C ₁₆ to C ₂₉ di (cyclohexyl) alkane of the general formula contains, in which «1 to 3, R ₁ and R _{2 are} hydrogen atoms or methyl radicals and R ₃ , R ₄ , R ₅ , R ₆ and R ₇