WO1999067347A2

WO1999067347A2 - Metallocene-catalyzed oligodecenes, their production and their use as component in lubricants

Info

Publication number: WO1999067347A2
Application number: PCT/EP1999/003809
Authority: WO
Inventors: Hans Peter Rath; Helmut Mach
Original assignee: Basf Aktiengesellschaft
Priority date: 1998-06-19
Filing date: 1999-06-02
Publication date: 1999-12-29
Also published as: DE19827323A1; WO1999067347A3; JP2002518582A; AU4504699A; EP1088049A2; KR20010053003A

Abstract

The invention relates to oligodecenes which are obtained by oligomerisation of linear 1-decene, whereby up to 40 mol %, in relation to the quantity of linear 1-decene, of other linear C8-C12-1-alkenes can be included by polymerization, in the presence of a titanium, zirconium or hafnium metallocene catalyst and an activator on a basis of aluminium-organic, boron-organic or carbo-cationic compounds, and which have possibly been hydrogenated following oligomerisation. Said oligodecenes have a number average molecular weight of between 500 and 200,000. The invention further relates to their use as components in lubricants, especially motor oils and transmission oils.

Description

METALLOCENE CATALYZES PRODUCED OLIGODECENES, THEIR PRODUCTION AND THEIR USE AS COMPONENTS IN LUBRICANTS

description

The present invention relates to the use of metallocene-catalyzed oligodecenes with a number-average molecular weight of 500 to 200,000 as components in lubricants, in particular in motor oils and gear oils, and to such lubricants themselves. Since some of these oligodecenes represent new substances, the invention relates to continue these new oligodecenes.

Hydrogenated short and medium chain oligoalkenes have long been used as components in synthetic lubricants, e.g. Motor oils, used. These are essentially di-, tri- and tetramers which are produced by oligomerization, for example using boron trifluoride as a catalyst and alcohols such as butanol or pentanol as promoters. However, this technology does not specifically lead to higher molecular weight oligomers terminated with vinylidene double bonds.

From OA 93/24539 (1) poly-1-olefins from C ₃ - to co-olefins such as propene, 1-butene, 1-pentene or 1-hexene with a number average molecular weight of 300 to 10,000 are known, which by conventional Metallocene catalysis can be produced. The 1-olefins mentioned are always used in a mixture with more volatile saturated and unsaturated hydrocarbons, for example a technical butane / butene stream or technical isobutene-containing butene streams (“raffinate 1/11” from the steam cracker) are used. The poly-1-olefins obtained are also suitable, inter alia, as a constituent for lubricants.

EP-A 613 873 (2) describes metallocene-catalyzed oligomers made from linear α-olefins having 8 to 20 C atoms, e.g. technical 1-octene or technical 1-dodecene, with a number average molecular weight of 400 to 3000. According to (2), such oligomers are generally suitable as a base material for lubricants, but no longer with a number average molecular weight of 6000 or more.

WO-A 96/28486 (3) relates to copolymers of unsaturated dicarboxylic acids or their anhydrides and oligomers of 1-olefins having 3 to 14 carbon atoms, which can be prepared by metallocene catalysis. Among other things, n-decene is also mentioned as the 1-olefin. The average molecular weight of the olefin oligo- mere is 300 to 10,000. The copolymers obtained from the unsaturated dicarboxylic acid (anhydrides) and the olefin oligomers are suitable as fuel and lubricant additives after derivatization with amines. 5

From WO-A 96/23751 (4), olefin oligomers produced by means of metallocene catalyst systems are known, which are based on linear and ring-shaped C 1 -C 1 -efins, for example 1-decene. Their weight average molecular weight (M _w ) is 100 to

10 20,000 with a molecular weight distribution M _W / M _N (weight average / number average) from 1.0 to 2.4. Their degree of polymerization is in the range from 2 to 200. According to (4), these olefin oligomers can be functionalized with the usual chemical reactions such as hydroformylation and / or hydroamination

Process 15 connections, which e.g. are suitable as fuel or lubricant additives.

The systems known from the prior art, however, only partially meet today's high requirements for components for 20 gear oils and engine oils and other lubricants, in particular the viscosity-temperature behavior is still in need of improvement.

The object of the present invention was to remedy the shortcomings of the prior art.

Accordingly, the use of oligodecenes, which was obtained by oligomerizing linear 1-decene, up to 40 mol%, based on the amount of linear 1-decene, was further linear

30 C ₈ "to Cι ₂ -1-alkenes can be polymerized in, are available in the presence of a titanium, zirconium or hafnium metallocene catalyst and an activator based on organoaluminum, organoboron or carbocationic compounds and then the oligomerization has been hydrogenated

35 can, with a number average molecular weight of 500 to 200,000, be found as components in lubricants, in particular in engine and gear oils, especially in multigrade engine oils and gear oils.

40 In addition to engine and gear oils, the areas of application for the oligodecenes mentioned are in particular hydraulic fluids, bed sheet oils, compressor oils, circulation oils, calender oils, rolling oils and lubricating greases.

In a preferred embodiment, the oligodecenes mentioned have a number average molecular weight (M _N ) of 10,000 to 200,000, preferably 20,000 to 150,000, in particular from 25,000 to 100,000, especially from 30,000 to 80,000, particularly preferably from 35,000 to 60,000, the determination of M _N usually being carried out by gel permeation chromatography (GPC), as a viscosity index improver in fully synthetic, partially synthetic and mineral motor oils, in particular in such multigrade engine oils, because they have a significantly more favorable flow behavior at high and especially at low temperatures. At low temperatures, for example at 0 to -30 ° C (start-up of the engine in frost), the engine oils remain more fluid; at high temperatures (operating temperature of the engine) they remain sufficiently viscous so that the lubricating film does not tear off.

(Fully) synthetic motor oils are to be understood in particular as those based on organic esters, synthetic hydrocarbons, poly-α-olefins and polyolefins (e.g. polyisobutene). Semi-synthetic motor oils are mixtures of mineral oils with synthetic motor oils, especially with the above-mentioned synthetic motor oils. The oligecenes mentioned can just as well be used in engine oils based only on mineral oils. Particularly interesting is the use in the so-called multi-grade engine oils, which are equally suitable for winter and summer operation of engines.

The engine oils mentioned can be used for a wide variety of applications, but in particular as four-stroke engine oils in automotive and two-wheel engines, locomotive diesel engines, etc.

In a further preferred embodiment, the oligodecenes mentioned have a number average molecular weight (M _N ) of 800 to 50,000, preferably from 1000 to 30,000, in particular from 1500 to 20,000, especially from 2000 to 15,000, the determination of M _N usually by gel permeation - Chromatography (GPC) is used as a thickener or viscosity index improver in gear oils, especially in multigrade gear oils. "Thickeners" and "viscosity improvers" are synonyms when used in gear oils. Gear oils are to be understood here in particular as gear oils for the automotive sector, especially manual and automatic gear oils. The oligodecenes have a very good thickening effect as well as high shear stability and very low low-temperature viscosities. The oligodecenes according to the application are clearly superior to the polymethacrylates normally used for such gear oils. In a further preferred embodiment, the said oligodecenes with a number average molecular weight (M _N ) of 500 to 5000, preferably from 650 to 3500, in particular from 800 to 2500, the determination of M _N usually being carried out by gel permeation chromatography (GPC) as synthetic Lubricant components in lubricants, especially in engine and gear oils, especially in multigrade engine and gear oils. As such engine and transmission oils, the above are normally considered. The oligodecenes are characterized by particularly low low-temperature viscosities and are clearly superior to the poly-α-olefins commonly used for this purpose. To increase the thermo-oxidative stability of such synthetic lubricating components, the oligodecenes according to the application are mostly used in their hydrogenated form, which, however, generally has no influence on the viscosimetic data.

The amount of the oligodecenes mentioned in the lubricants, in particular in the motor oils or gear oils, is usually 0.1 to 95% by weight, in particular 0.5 to 90% by weight, especially 1 to 85% by weight, based on the lubricant or the engine oil or gear oil. When used as a viscosity index improver in motor oils, the preferred amount used is 0.1 to 40% by weight, in particular 0.5 to 20% by weight, especially 1 to 10% by weight, based on the motor oil. When used as a thickener (viscosity index improver) in gear oils, the preferred amount used is 0.5 to 70% by weight, in particular 1 to 50% by weight, especially 5 to 40% by weight, based on the gear oil. When used as a synthetic lubricating component in lubricants such as engine and gear oils, the preferred amount is 1 to 95% by weight, in particular 5 to 90% by weight, especially 20 to 85% by weight, particularly preferably 30 to 85 % By weight, very particularly preferably 40 to 85% by weight, based on the lubricant. Other customary additives such as dispersants, corrosion inhibitors, wear protection components, detergents, antioxidants, friction modifiers and / or defoamers (foam inhibitors) may also be present in the lubricants or engine or gear oils in the amounts customary for this.

The essential monomer component in the oligodecenes mentioned is linear 1-decene, which alone or in a mixture with up to 40 mol%, in particular up to 20 mol%, especially up to 5 mol%, based on the amount of 1- Decene, further linear CQ - until Cι ₂ -1-alkenes (1-octene, 1-nonen, 1-undecene and / or 1-dodecene) can be oligo erized. These 1-alkenes can be in chemically pure form (purities of usually 99 to 99.9% by weight) or as industrial mixtures in purities of usually 90 up to 99% by weight are used, the remaining constituents of the technical mixtures normally being approximately equally volatile, polymerizable or non-polymerizable components (for example unsaturated isomers, homologs or saturated hydrocarbons). As a rule, the 1-alkenes used are practically free of volatile components, especially free of more volatile saturated or unsaturated hydrocarbons, in particular those with fewer than 8 carbon atoms; practically free means that at most a proportion of such volatile components of less than 1% by weight, in particular less than 0.5% by weight, can occur.

The systems of metallocene catalyst and active gate used for oligomerization are conventional catalyst systems. The desired molecular weight ranges of the oligodecenes can be adjusted in a known manner by varying the structure of the metallocene. The oligomerization is usually carried out in a suitable medium ("reaction mixture"), e.g. an organic solvent, under the usual conditions for this.

No special requirements are imposed on the catalyst systems, except that they are largely soluble in the reaction mixture. The reaction mixture is the mixture which is present in the time after all the reaction components have been combined until the catalyst system has been destroyed after the oligomerization reaction has taken place.

The solubility of the catalyst system in the reaction mixture is analogous by measuring the turbidity of the reaction mixture

DIN 38404 determined. The catalyst system is largely soluble if the turbidity number is in the range from 1 to 10, preferably in the range from 1 to 3.

The metallocene component of the catalyst system is a complex of titanium, zirconium and hafnium in which the metal atom M is sandwiched between two optionally substituted cyclopentadienyl groups, the remaining valences of the central atom M being replaced by easily exchangeable leaving atoms or leaving groups X ¹ , X ² are saturated.

Suitable metallocene complexes are those with the general formula Cp ₂ MX ¹ X ² , in which M is titanium, zirconium or hafnium, preferably zirconium. Cp ₂ represent a pair of optionally substituted cyclopentadienyl ligands. Both cyclopentadienyl ligands or only one of the two can be substituted.

In the event that the substituents are C ₅ to C ₃ o-alkyl groups, the cyclopentadienyl rings are usually substituted symmetrically. This means that the type, number and also the position of the alkyl substituents of one Cp ring is identical to the type, number and also position of the alkyl substituents of the second Cp ring. The number of alkyl groups per cyclopentadienyl ring is 1 to 4.

Suitable C ₅ - to C ₃ o-alkyl radicals are the aliphatic radicals pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octa-decyl, nonadecyl and eicosyl and their isomers , such as neo-pentyl, iso-octyl, and the cycloaliphatic radicals cyclopentyl and cyclohexyl. N-Octadecyl is particularly suitable.

The optionally C ₅ - to C ₃ o-alkyl-substituted cyclopentadienyl units can, however, also be substituted by 1 to 2 C ₄ - to cio-alkylene units, which together with the cyclopentadienyl unit form a fused ring system, such as the tetrahydroindenyl system, form.

However, those pairs in which at least one cyclopentadienyl unit is substituted with at least one organosilyl group -Si (R ¹ ) _{3 are also} suitable as substituted cyclopentadienyl ligands. R ¹ then denotes a Ci to C ₃ cr -organic group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl , i-pentyl, neo-pentyl, hexyl, heptyl, octyl, nonyl, cyclohexyl, phenyl or p-tolyl. Preferred organosilyl radicals are trimethylsilyl and tert. -Butyldimethylsilyl, especially trimethylsilyl.

In the case of organosilyl substitution on the cyclopentadienyl units, the symmetrical substitution pattern is not absolutely necessary, but is also not excluded.

Of particular interest are those metallocene catalysts in which the two cyclopentadienyl ligands are connected to one another via a bridge member. Such bridging links mostly have 1 to 4 atoms (C atoms and / or heteroatoms such as Si, N, P, 0, S, Se or B) and optionally alkyl chains, for example 1,2-ethylidene, 1,3-propylidene or dialkylsilane -Bridges. Easily exchangeable, formally negatively charged leaving atoms or leaving groups X ¹ , X ^{2 of} the metallocene complexes of the general formula CpMX ¹ X ² may be mentioned: hydrogen, halogen such as fluorine, bromine, iodine and preferably chlorine. The following may also be mentioned: alcoholates such as methanolate, ethanolate, n- and i-propanolate, phenolate, trifluoromethylphenolate, naphtholate and silanolate.

Furthermore, particularly suitable for X ¹ , X ^{2 are} aliphatic Ci to Cio alkyl radicals, in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neo -Pentyl, hexyl, preferably methyl, tert-butyl and neo-pentyl, furthermore alicyclic C ₃ - to -CC hydrocarbon radicals such as cyclopropyl, cyclobutyl, cyclopentyl and in particular cyclohexyl or C ₅ - to C ₂ Q-bicycloalkyl such as bicyclopentyl and especially bicycloheptyl and bicyclooctyl.

Examples of substituents X ¹ , X ² with aromatic structural units are C ₆ - to cis-aryl, preferably phenyl or naphthyl, alkyl - aryl or arylalkyl, each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, such as for example tolyl and benzyl.

Individual examples of suitable metallocene complexes are: bis (n-octadecylcyclopentadienyl) zirconium dichloride, bis (trimethylsilyl-cyclopentadienyl) zirconium dichloride, bis (tetrahydroindenyl) zirconium dichloride, bis [(tert-butyldimethyladilium) dichloride). Bis (di-tert-butylcyclopentadienyl) zirconium dichloride, (ethylidene bisindenyl) zirconium dichloride, ethylidene bis (tetrahydroindenyl) zirconium dichloride and bis [3,3 (2-methyl-benzindenyl)] dimethylsilanediyl zirconium dichloride.

The metallocene complexes mentioned can be easily prepared by known processes, e.g. Brauer (ed.): Handbuch der Preparative Inorganic Chemistry, Volume 2, 3rd edition, pages 1395 to 1397, Enke, Stuttgart 1978. A preferred process is based on the lithium salts of the appropriately substituted cyclopentadienyls, which are reacted with the transition metal halides.

Only one metallocene complex is expediently used in the oligomerization reaction, but it is also possible to use mixtures of different metallocene complexes.

In addition to the metallocene complexes, the catalyst systems also contain activators which are known per se and are also called cocatalysts in the literature. They generally alkylate them Transition metal component of the catalyst system and / or abstract a ligand X from the transition metal component, so that ultimately a catalyst system for the oligomerization of olefinically unsaturated hydrocarbons can arise. Organometallic compounds of the 1st to 3rd main group or the 2nd subgroup of the periodic table are generally suitable for this task, but other acceptor compounds such as, for example, carbocation salts can also be used.

In the present case, suitable activator compounds are organoaluminum and organoboron compounds as well as carbocation salts. Preference is given to open-chain or cyclic oligomeric alumoxane compounds which can be obtained by reacting aluminum tri-alkylene, in particular trimethyl or triethyl aluminum, with water.

Also suitable as cocatalysts are generally aluminum organyls of the general formula A1 (R ² ) ₃ , where R ^{2 is} hydrogen, C ₁ -C ₄ -alkyl, preferably C 1 -C ₄ -alkyl, in particular methyl, ethyl or butyl. In addition, R ^{2 can} also represent arylalkyl or alkylaryl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical.

Aluminum alkyls Al (R ² ) _{3 are} furthermore suitable, in which R ² can mean fluorine, chlorine, bromine or iodine in addition to the radicals defined above, with the proviso that at least one radical R ^{2 is} a C-organic radical or a hydrogen atom . Particularly preferred compounds are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, di-isobutyl aluminum hydride and diethyl aluminum chloride.

In addition, organic boron compounds are also very suitable as activators, for example tris -arylboron compounds, preferably tris (pentafluoropheny1) boron, furthermore salts of carbonium ions, preferably triphenylmethyltetraarylborate, in particular triphenylmethyltetra (pentafluorophenyD orate.

The Al, B or C compounds mentioned are known or can be obtained in a manner known per se.

As activators, they can be used alone or as mixtures in the catalyst system. The activator component is preferably used in a molar excess with respect to the metallocene complex. The molar ratio of activator to metallocene complex is generally 100: 1 to 10,000: 1, preferably 100: 1 to 1,000: 1:

The constituents of the catalyst systems described can be introduced into the oligomerization reactor individually or as a mixture in any order. The metallocene complex is preferably mixed with at least one activator component before it enters the reactor, that is to say preactivated.

The oligodecenes can be prepared in the customary reactors used for the oligomerization of olefins, either batchwise or preferably continuously. Suitable reactors include continuously operated stirred kettles, it also being possible to use a series of several stirred kettles connected in series.

The oligomerization can be carried out in a suspension, in liquid monomers and in inert solvents. In the case of oligomerization in solvents, in particular liquid organic hydrocarbons such as benzene, ethylbenzene or toluene are used. The oligomerizations are preferably carried out in a reaction mixture in which the liquid monomer is present in excess.

Since the oligomerization is generally carried out at temperatures from -20 ° C to 200 ° C, in particular from 0 to 140 ° C, especially at 30 ° C to 110 ° C, it can usually be carried out using the low-pressure or medium-pressure process . The amount of catalyst used is not critical.

The oligodecenes produced by metallocene catalysis contain unsaturated double bonds due to the oligomerization mechanism; the proportion of terminal vinylidene double bonds is particularly high. If these double bonds interfere when used as motor oil or lubricating oil components, they can be converted into saturated structures by conventional hydrogenation processes.

The oligodecenes used according to the invention have the above-mentioned number average molecular weight (M _N ). The number average molecular weight is usually determined by gel permeation chromatography (GPC). The molecular weight distribution M _W / M _N (weight average / number average) is generally 1.3 to 5, a narrow distribution being more widely distributed, for example by extraction processes Samples are created and a broad distribution can also be obtained by mixing. If uniform catalyst systems are used, the distribution is generally from 1.5 to 3.0. Under certain circumstances, a broader distribution can be more advantageous, because the same thickening effect in the engine or lubricating oil usually requires more oligomer with a narrow distribution and the same molecular weight. A wide distribution with a low-molecular flank in the molecular weight distribution can also be advantageous for an often additionally occurring dispersing action in the motor or lubricating oil. Furthermore, bimodal distributions generated by blends can also have an advantageous effect. Narrower distributions can also be advantageous due to better shear stability, especially with gear oils.

Since some of the oligodecenes described (namely those with a number average molecular weight from 30,000) are new substances, the present invention further relates to oligodecenes which are obtained by oligomerizing linear 1-decene, up to 40 mol%, based on the amount of linear 1-Decene, further linear Cs to Cι -1 olefins can be polymerized in, are available in the presence of a titanium, zirconium or hafnium metal locene catalyst and an activator based on organoaluminum, organic boron or carbocationic compounds may have been hydrogenated after the oligomerization, with a number average molecular weight of 30,000 to 200,000, in particular from 35,000 to 150,000.

The present invention also relates to a process for the preparation of these oligodecenes, which is characterized in that linear 1-decene or a mixture of linear 1-decene and up to 40 mol%, based on the amount of linear 1-decene, further linear CQ - to Cχ ₂ -1-alkenes metallocene-catalysed - as described above - oligomerized and, if desired, hydrogenated subsequently.

The following examples are intended to explain the present invention further, but are not to be understood as a limitation. Unless otherwise stated, percentages always refer to the weight. Manufacturing examples

Example 1:

Synthesis of an oligodecene with M _N = 11,400

400 ml of linear 1-decene (polymer quality, 99.8%) were placed in a 1 l stirred autoclave with a double jacket made of V4A steel and heated to 50.degree. In a Schlenk vessel, 44 mg of [ethylidene bis (tetrahydroindenyl)] zirconium dichloride were dissolved in 43.8 ml of methylalumoxane (10% in n-hexane), pressed into the reactor in portions with nitrogen and rinsed with 30 ml of ethylbenzene . The portioning was carried out in such a way that the cryostat which removed the heat of reaction was not overloaded and was able to maintain the reaction temperature at 50.degree. There was a temperature difference between the jacket and the reactor contents of max. 40 ° C, which subsided within 2 to 3 hours. After 4 hours, the mixture was cooled to room temperature, the autoclave was emptied and diluted with aliquots of cyclohexane. It was washed with 100 ml of 0.1% sulfuric acid and twice with 100 ml of demineralized water, dried over Na ₂ S0 ₄ and distilled out to 225 ° C (2 mbar). The bottom product had a viscosity of 1100 mm ² / s (100 ° C.) and an M _N according to GPC of 11,400. The yield was 85%, the vinylidene double bond content 94%.

Example 2:

Synthesis of an oligodecene with M _N = 45,000

Analogous to Example 1, linear 1-decene (99.8%) was oligomerized in the presence of bis [3, 3 (2-methylbenzindenyl)] dimethylsilanediylzirconium dichloride in methylalumoxane to give an oligodecene with an M _N according to GPC of 45,000 .

Example 3:

Synthesis of an oligodecene with M _N = 3500

Analogously to Examples 1 and 2, an oligodecene with an M _N according to GPC of 3500 was produced using bis (n-octadecylcyclopentadienyl) zirconium dichloride / methylalumoxane.

Example 4:

Synthesis of an oligodecene with M _N = 6450

Analogously to Examples 1 and 2, an oligodecene with an M ^ according to GPC of 6450 was prepared using bis (n-octadecylcyclopentadienyl) zirconium dichloride / methylalumoxane. Example 5:

Synthesis of an oligodecene with M _N = 850

Analogously to Examples 1 and 2, an oligodecene with an M _N according to GPC of 850 was produced using bis (n-octadecylcyclopentadienyl) zirconium dichloride / methylalnmoxane.

Examples of use

Example A:

Testing the viscosity-temperature behavior of a mineral multigrade engine oil with an oligodecene MN = 45,000 as a viscosity index improver

A solvent-refined multigrade motor oil (15W / 40) on a common mineral oil basis, which contained the following common additives:

Ashless dispersants 5.0% usual overbased sulfonate 2.8% zinc dithiophosphate 2.0% common antioxidant 0.4% common friction modifier 0.1% common foam inhibitor 0.002

was mixed with the oligodecene from Example 2 (M _N = 45,000) as a viscosity index improver in the amounts given below. The results of the viscosity determinations are summarized in Table 1:

Table 1

In all four measurements, the values required by the standards set by the mineral oil industry were reached or even exceeded in the sense of over-performance. Example B

Testing the viscosity-temperature behavior and the shear behavior of a multigrade gear oil with an oligodecene M _N = 3500 and M _N = 6450 as a thickener

A multigrade gearbox oil of the composition given in Table 2 was mixed with two different oligodecenes (M _N = 3500 from Example 3 and M _N = 6450 from Example 4 / Bl and B2) and for comparison with a conventional polymethacrylate (B3) as a thickener ( Viscosity index improver) mixed and examined for its viscosity and shear behavior. The results are summarized in Table 2:

Table 2

* The package of the usual additives was the same for the three tests B1 to B3 and essentially contained wear protection components based on nitrogen-phosphorus, antioxidants and corrosion protection components.

The standardization of the three gear oils Bl to B3 required for comparability was achieved by setting them to the same viscosity at 100 ° C, which is why the amounts of thickeners used also differ. It can be seen from the values for the viscosity at -40 ° C that B2 is clearly superior to the comparative oil B3. From the values for the shear loss it can be seen that B1 is clearly superior to the comparative oil B3, B2 and B3 having approximately the same effect. Depending on the requirement profile for the gear oil, you can fine-tune the molecular important more affect the low-temperature viscosity behavior or more the shear behavior in the desired manner.

Example C

Testing the viscosity-temperature behavior of a fully synthetic multi-grade engine oil with an oligodecene M _N = 850 as a synthetic lubricating component

A fully synthetic multigrade motor oil (5W / 40) with the following composition:

synthetic lubricant 56.15% diisononyl adipate 25.0%

Viscosity index improvers 1.2% based on styrene / butadiene, customary additives (ash-free 17.75% dispersants, detergents based on sulfonate, zinc dithiophosphate, antioxidant, friction modifier, foam inhibitor) were used with the oligodecene from Example 5 (M _N = 850 / CD and for comparison with the same amount of poly-α-olefin (viscosity: 8mm ² / s / C2) as a synthetic lubricating component for its viscosity behavior, the results are summarized in Table 3:

Table 3

The values show the clear superiority of CI over the comparison oil C2. Example D

Testing the viscosity-temperature behavior of a partially synthetic multi-grade gear oil with an oligodecene M _N = 850 as a synthetic lubricating component

A semi-synthetic multi-grade automatic transmission oil with the following composition:

usual mineral oil 32.5% synthetic lubricant 56.85% usual additives analogous to 5.6% play B (*)

Polyisobutene (M _N = 2300) as 3.85% thickener common polymethacrylate as 1.0% thickener common pour point improver 0.2%

was examined for the viscosity behavior with the oligodecene from Example 5 (M = 850 / Dl) and for comparison with the same amount of poly-α-olefin (viscosity: 8 mm ² / s / D2) as a synthetic lubricant component. The results are summarized in Table 4:

Table 4

The comparison of the values at -40 ° C shows the clear superiority of Dl compared to the comparison oil D2.

Claims

claims

1. Use of oligodecenes which can be copolymerized by oligomerizing linear 1-decene, up to 40 mol%, based on the amount of linear 1-decene, of further linear C 1 -C ₂ -alkenes Presence of a titanium, zirconium or hafnium metallocene catalyst and an activator based on organoaluminum, organoboron or carbocationic compounds are available and may have been hydrogenated after the oligomerization, with a number average molecular weight of 500 to 200,000 as components in lubricants .

2. Use of oligodecenes according to claim 1 with a number average molecular weight of 10,000 to 200,000 as viscosity index improvers in multigrade motor oils.

3. Use of oligodecenes according to claim 1 with a number-average molecular weight of 800 to 50,000 as a thickener in multigrade gear oils.

4. Use of oligodecenes according to claim 1 with a number average molecular weight of 500 to 5000 as synthetic see lubricant component in lubricants.

5. Lubricants with a content of 0.1 to 95% by weight, based on the lubricant, of oligodecenes according to claim 1.

6. Oligodecenes, which can be copolymerized by oligomerizing linear 1-decene, with up to 40 mol%, based on the amount of linear 1-decene, of further linear Cs to Cι ₂ -l-01efins in the presence of a Titanium, zirconium or hafnium metallocene catalyst and an activator based on organoaluminum, organoboron or carbocationic compounds are available and may have been hydrogenated after the oligomerization, with a number average molecular weight of 30,000 to 200,000.

7. A process for the preparation of oligodecenes according to claim 6, characterized in that linear 1-decene or a mixture of linear 1-decene and up to 40 mol%, based on the amount of linear 1-decene, further linear CQ - to Cι ₂ -1-alkenes metallocene catalyzed oligomerized and, if desired, then hydrogenated.