EP0422019B1 - Olefinoligomere mit schmierungseigenschaften und verfahren zu ihrer herstellung - Google Patents

Olefinoligomere mit schmierungseigenschaften und verfahren zu ihrer herstellung Download PDF

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EP0422019B1
EP0422019B1 EP89905983A EP89905983A EP0422019B1 EP 0422019 B1 EP0422019 B1 EP 0422019B1 EP 89905983 A EP89905983 A EP 89905983A EP 89905983 A EP89905983 A EP 89905983A EP 0422019 B1 EP0422019 B1 EP 0422019B1
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composition
molecular weight
catalyst
oligomers
decene
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EP0422019A4 (de
EP0422019A1 (de
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Margaret May-Som Wu
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ExxonMobil Oil Corp
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Mobil Oil Corp
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Priority claimed from US07/210,434 external-priority patent/US4827073A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties

Definitions

  • This invention relates to novel lubricant compositions and more particularly, to novel synthetic lubricant compositions prepared from alpha-olefins, or 1-alkenes.
  • the invention specifically relates to novel synthetic lubricant compositions from 1-alkenes exhibiting superior viscosity indices and other improved characteristics essential to useful lubricating oils.
  • This invention further relates to a process for manufacturing such lubricant compositions.
  • PAO polyalpha-olefin
  • the oligomerization of 1-decene, for example, to lubricant oligomers in the C30 and C40 range can result in a very large number of structural isomers. Henze and Blair,J.A.C.S. 54,1538, calculate over 60 x1012 isomers for C30-C40. Discovering exactly those isomers, and the associated oligomerization process, that produce a preferred and superior synthetic lubricant meeting the specification requirements of wide-temperature fluidity while maintaining low pour point represents a prodigious challenge to the workers in the field. Brennan, Ind. Eng. Chem. Prod. Res. Dev.
  • 1-decene trimer as an example of a structure compatible with structures associated with superior low temperature fluidity wherein the concentration of atoms is very close to the center of a chain of carbon atoms. Also described therein is the apparent dependency of properties of the oligomer on the oligomerization process, i.e., cationic polymerization or Ziegler-type catalyst, known and practiced in the art.
  • One characteristic of the molecular structure of 1-alkene oligomers that has been found to correlate very well with improved lubricant properties in commercial synthetic lubricants is the ratio of methyl to methylene groups in the oligomer.
  • the ratio is called the branch ratio and is calculated from infra red data as discussed in "Standard Hydrocarbons of High Molecular Weight", Analytical Chemistry , Vol.25, no. 10, p.1466 (1953). Viscosity index has been found to increase with lower branch ratio.
  • oligomeric liquid lubricants exhibiting very low branch ratios have not been synthesized from 1-alkenes.
  • oligomers prepared from 1-decene by either cationic polymerization or Ziegler catalyst polymerization have branch ratios of greater than 0.20.
  • Shubkin, Ind. Eng.Chem. Prod. Res. Dev. 1980, 19, 15-19, provides an explanation for the apparently limiting value for branch ratio based on a cationic polymerization reaction mechanism involving rearrangement to produce branching.
  • Other explanations suggest isomerization of the olefinic group in the one position to produce an internal olefin as the cause for branching.
  • US-A-4,282,392 to Cupples et al. discloses an alpha-olefin oligomer synthetic lubricant having an improved viscosity-volatility relationship and containing a high proportion of tetramer and pentamer via a hydrogenation process that effects skeletal rearrangement and isomeric composition.
  • the composition claimed is a trimer to tetramer ratio no higher than one to one. The branch ratio is not disclosed.
  • US-A-3 206 523 discloses compositions which differs from those of the invention in that the branch ratio is higher than 0.16.
  • Liquid hydrocarbon lubricant compositions have been obtained from C6-C20, preferably C8-C12, 1-alkene oligomerization that exhibit surprisingly high viscosity index (VI) while, equally surprisingly, exhibit very low pour points.
  • the compositions comprise C30-C1300 hydrocarbons, the compositions having a branch ratio of between 0.1 and 0.16; weight average molecular weight between 300 and 45,000; number average molecular weight between 300 and 18,000; molecular weight distribution between 1 and 5 and pour point below -15°C.
  • the hydrocarbons comprise alkanes or alkenes.
  • the compositions have a viscosity index greater than 130 and viscosity at 100°C between 3mm2/s and 750 mm2/s.
  • compositions have been found to exhibit superior lubricant properties either alone or in a mixture with 9-methyl,11-octylheneicosane.
  • the mixture has a viscosity index of greater than 130, preferably from 130 to 280, while maintaining a pour point less than -15°C.
  • These compositions are representative of the instant invention comprising C30H62 alkanes having a branch ratio, or CH3/CH2 ratio, of between 0.10 and 0.16.
  • compositions of the invention referred to herein as polyalpha-olefin or HVI-PAO, conferring upon the compositions especially high viscosity indices in comparison to commercially available polyalpha-olefin (PAO) synthetic lubricants.
  • PAO polyalpha-olefin
  • Unique lubricant oligomers of the instant invention an also be made in a wide range of molecular weights and viscosities comprising C30 to C1000 hydrocarbons having a branch ratio of between 0.10 and 0.16 and molecular weight distribution of about 1.05 to 2.5.
  • the oligomers can be mixed with conventional mineral oils or greases of other properties to provide compositions also possessing outstanding lubricant properties.
  • compositions of the present invention comprise the polymeric residue of 1 alkenes taken from linear C6-C20, preferably C8-C12, alkenes and can be prepared by the oligomerization of alpha-olefins such as 1-decene under oligomerization conditions in contact with a supported and reduced valence state metal oxide catalyst from Group VIB of the IUPAC Periodic Table. Chromium oxide is the preferred metal oxide.
  • the composition can be hydrogenated.
  • the polymeric residue comprises poly 1-decene having a molecular weight of about 422, a viscosity index of about 134 and a pour point of less than -45°C.
  • the present invention provides a process for producing liquid oligomers of olefins, such as 1-decene, with branch ratios of between 0.10 and 0.16 and having higher viscosity indices than oligomers with higher branch ratios.
  • oligomers with low branch ratios can be used as basestocks for many lubricants or greases with an improved viscosity-temperature relationship, oxidative stability, volatility, etc. They can also be used to improve viscosities and viscosity indices of lower quality oils.
  • the olefins can, for example, be oligomerized over a supported and reduced metal oxide catalyst from Group VIB of the Periodic Table to give oligomers suitable for lubricant application.
  • the instant application is directed to a process for the oligomerization of olefinic hydrocarbons containing 6 to 20 carbon atoms which comprises oligomerizing said hydrocarbon under oligomerization conditions, wherein the reaction product consists essentially of substantially non-isomerized olefins.
  • Oligomerization conditions comprise a temperature of 90°C to 250°C, preferably 100°C to 180°C, with a chromium catalyst on a porous support which catlyst has been treated by oxidation at a temperature of 200°C to 900°C in the presence of an oxidizing gas and then by treatment with a reducing agent, such as CO, at a temperature and for sufficient time to reduce the catalyst to a lower valence state.
  • a reducing agent such as CO
  • alpha olefins such as 1-decene, and wherein a major proportion of the double bonds of the olefins or olefinic hydrocarbons are not isomerized, in the presence of a suitable catalyst, e.g., a supported and reduced metal oxide catalyst from Group VIB of the Periodic Table.
  • a suitable catalyst e.g., a supported and reduced metal oxide catalyst from Group VIB of the Periodic Table.
  • the yield of the C30+ oligomer is at least 85 wt% for product having a viscosity of at least 15 mm2/s at 100°C.
  • the catalyst is not subjected to a further oxidation step after the reduction.
  • the olefin comprises 1-decene and the oligomer has a VI of 181 or greater and a branch ratio of 0.14 to 0.16.
  • Figure 1 is a comparison of PAO and HVI-PAO syntheses.
  • Figure 3 shows pour points for PAO and HVI-PAO
  • Figure 4 shows C-13 NMR spectra for HVI-PAO from 1-hexene.
  • Figure 5 shows C-13 NMR spectra of 5 mm2/s HVI-PAO from 1-decene.
  • Figure 6 shows C-13 NMR spectra of 50 mm2/s HVI-PAO from 1-decene.
  • Figure 7 shows C-13 NMR spectra of 145 mm2/s HVI-PAO from 1-decene.
  • Figure 8 shows the gas chromatograph of HVI-PAO 1-decene trimer.
  • Figure 9 shows C-13 NMR of HVI-PAO trimer of 1-decene.
  • Figure 10 shows C-13 NMR calculated vs. observed chemical shifts for HVI-PAO 1-decene trimer components.
  • HVI-PAO oligomers or lubricants refer to hydrogenated oligomers and lubricants in keeping with the practice well known to those skilled in the art of lubricant production.
  • HVI-PAO oligomers are mixtures of dialkyl vinyledenic and 1,2 dialkyl or trialkyl mono-olefins.
  • Lower molecular weight unsaturated oligomers are preferably hydrogenated to produce thermally and oxidatively stable, useful lubricants.
  • Higher molecular weight unsaturated HVI-PAO oligomers are sufficiently thermally stable to be utilized without hydrogenation and, optionally, may be so employed.
  • Both unsaturated and hydrogenated HVI-PAO of lower or higher molecular exhibit viscosity indices of at least 130, preferably from 130 to 280, and pour point below -15°C, preferably -45°C.
  • HVI-PAO high viscosity index polyalphaolefins
  • PAO polyalphaolefins
  • the HVI-PAO produced in the present invention has a structure with a CH3/CH2 ratio ⁇ 0.19 compared to a ratio of >0.20 for PAO.
  • Figure 2 compares the viscosity index versus viscosity relationship for HVI-PAO and PAO lubricants, showing that HVI-PAO is distinctly superior to PAO at all viscosities tested.
  • HVI-PAO oligomers as shown by branch ratio that results in improved viscosity index (VI)
  • VI viscosity index
  • oligomers of regular structure containing fewer isomers would be expected to have higher solidification temperatures and higher pour points, reducing their utility as lubricants. But, surprisingly, such is not the case for HVI-PAO of the present invention.
  • Figure 2 and 3 illustrate superiority of HVI-PAO in terms of both pour point and VI.
  • MWD Molecular weight distributions
  • HVI-PAO of the present invention has been found to have a higher proportion of higher molecular weight polymer molecules in the product.
  • Viscosities of the novel HVI-PAO oligomers measured at 100°C range from 3 mm2s(cs) to 5000 mm2/s(cs).
  • novel oligomer compositions disclosed herein have been examined to define their unique structure beyond the important characteristics of branch ratio and molecular weight already noted. Dimer and trimer fractions have been separated by distillation and components thereof further separated by gas chromatography. These lower oligomers and components along with complete reaction mixtures of HVI-PAO oligomers have been studied using infra-red spectroscopy and C-13 NMR. The studies have confirmed the highly uniform structural composition of the products of the invention, particularly when compared to conventional polyalphaolefins produced by BF3, AlCl3 or Ziegler-type catalysis.
  • 1-hexene HVI-PAO oligomers of the present invention have been shown to have a very uniform linear C4 branch and contain regular head-to-tail connections.
  • the backbone structures have some head-to-head connection, indicative of the following structure as confirmed by NMR:
  • the NMR poly(1-hexene) spectra are shown in Figure 4.
  • the oligomerization of 1-decene by reduced valence state, supported chromium also yields a HVI-PAO with a structure analogous to that of 1-hexene oligomer.
  • the lubricant products after distillation to remove light fractions and hydrogenation have characteristic C-13 NMR spectra.
  • Figures 5, 6 and 7 are the C-13 NMR spectra of typical HVI-PAO lube products with viscosities of 5 mm2/s(cs), 50 mm2/s(cs) and 145 mm2/s(cs) at 100°C.
  • Table A presents the NMR data for Figure 5
  • Table B presents the NMR data for Figure 6
  • Table C presents the NMR data for Figure 7.
  • Table A (Fig. 5) Point Shift(ppm) Intensity Width(Hz) 1 79.096 138841. 2.74 2 74.855 130653. 4.52 3 42.394 148620. 6.68 4 40.639 133441. 37.6 5 40.298 163678. 32.4 6 40.054 176339. 31.2 7 39.420 134904.
  • 37.4 8 37.714 445452. 7.38 9 37.373 227254. 157 10 37.081 145467. 186 11 36.788 153096. 184 12 36.593 145681. 186 13 36.447 132292.
  • the novel oligomers have the following regular head-to-tail structure where n can be 3 to 17, x is 5 to 500: with some head-to-head connections. Preferably, n is 7 and average x is at least 15.
  • the oligomers have a viscosity index greater than 130 and a pour point less than -15°C.
  • the trimer of 1-decene HVI-PAO oligomer is separated from the oligomerization mixture by distillation from a 20 mm2/s(cs) as-synthesized HVI-PAO in a short-path apparatus in the range of 165-210°C at 13.3-26.6 Pa (0.1-0.2 torr).
  • the components were identified as 9-methyl,11-octylheneicosane and 11- octyldocosane by infra-red and C-13 NMR analysis and were found to be present in a ratio between 1:10 and 10:1, preferably between 1:2 and 2:1, heneicosane to docosane.
  • the hydrogenated 1-decene trimer produced by the process of this invention has an index of refraction at 60°C of 1.4396.
  • the process of the present invention produces a surprisingly simpler and useful dimer compared to the dimer produced by 1-alkene oligomerization with BF3 or AlCl3 as commercially practiced.
  • 1-decene dimer of the invention has been found to contain only three major components, as determined by GC.
  • the unhydrogenated components were found to be 8-eicosene, 9-eicosene, 2-octyldodecene and 9-methyl-8 or 9-methyl-9-nonadecene.
  • the hydrogenated dimer components were found to be n-eicosane and 9-methylnonacosane.
  • Olefins suitable for use as starting material in the invention include those olefins containing from 2 to about 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene and branched chain isomers such as 4-methyl-1-pentene. Also suitable for use are olefin-containing refinery feedstocks or effluents.
  • the olefins used in this invention are preferably alpha olefinic as for example 1-heptene to 1-hexadecene and more preferably 1-octene to 1-tetradecene, or mixtures of such olefins.
  • Oligomers of alpha-olefins in accordance with the invention have a low branch ratio of between 0.1 and 0.16 and superior lubricating properties compared to the alpha-olefin oligomers with a high branch ratio, as produced in all known commercial methods.
  • This new class of alpha-olefin oligomers are prepared by oligomerization reactions in which a major proportion of the double bonds of the alphaolefins are not isomerized.
  • These reactions include alpha-olefin oligomerization by supported metal oxide catalysts, such as Cr compounds on silica or other supported IUPAC Periodic Table Group VIB compounds.
  • the catalyst most preferred is a lower valence Group VIB metal oxide on an inert support.
  • Preferred supports include silica, alumina, titania, silica alumina, magnesia and the like.
  • the support material binds the metal oxide catalyst. Those porous substrates having a pore opening of at least 40 x 10 ⁇ 4 ⁇ m are preferred.
  • the support material usually has high surface area and large pore volumes with average pore size of 40 to 350 x 10 ⁇ 4 ⁇ m.
  • the high surface area are beneficial for supporting large amount of highly dispersive, active chromium metal centers and to give maximum efficiency of metal usage, resulting in very high activity catalyst.
  • the support should have large average pore openings of at least 40 x 10 ⁇ 4 ⁇ m, with an average pore opening of 60 to 300 x 10 ⁇ 4 ⁇ m being preferred. This large pore opening will not impose any diffusional restriction of the reactant and product to and away from the active catalytic metal centers, thus further optimizing the catalyst productivity.
  • a silica support with good physical strength is preferred to prevent catalyst particle attrition or disintegration during handling or reaction.
  • the supported metal oxide catalysts are preferably prepared by impregnating metal salts in water or organic solvents onto the support. Any suitable organic solvent known to the art may be used, for example, ethanol,methanol, or acetic acid.
  • the solid catalyst precursor is then dried and calcined at 200 to 900°C by air or other oxygen-containing gas. Thereafter the catalyst is reduced by any of several various and well known reducing agents such as, for example, CO, H2, NH3, H2S, CS2, CH3SCH3, CH3SSCH3,metal alkyl containing compounds such as R3Al, R3B,R2Mg, RLi, R2Zn, where R is alkyl, alkoxy, aryl and the like. Preferred are CO or H2 or metal alkyl containing compounds.
  • the Group VIB metal may be applied to the substrate in reduced form, such as CrII compounds.
  • the resultant catalyst is very active for oligomerizing olefins at a temperature range from below room temperature to about 250°C, preferably 90°-250°C, most preferably 100°- 180°C, at a pressure of 10.1 kPa (0.1 atmosphere) to 34500 kPa (5000 psi).
  • Contact time of both the olefin and the catalyst can vary from one second to 24 hours.
  • the weight hourly space velocity (WHSV) is 0.1 to 10, based on total catalyst weight.
  • the catalyst can be used in a batch type reactor or in a fixed bed, continuous-flow reactor.
  • the support material may be added to a solution of the metal compounds, e.g., acetates or nitrates, etc., and the mixture is then mixed and dried at room temperature.
  • the dry solid gel is purged at successively higher temperatures to 600°C for a period of 16 to 20 hours.
  • the catalyst is cooled down under an inert atmosphere to a temperature of 250 to 450°C and a stream of pure reducing agent is contacted therewith for a period when enough CO has passed through to reduce the catalyst as indicated by a distinct color change from bright orange to pale blue.
  • the catalyst is treated with an amount of CO equivalent to a two-fold stoichiometric excess to reduce the catalyst to a lower valence CrII state.Finally the catalyst is cooled down to room temperature and is ready for use.
  • the product oligomers have a very wide range of viscosities with high viscosity indices suitable for high performance lubrication use.
  • the product oligomers also have atactic molecular structure of mostly uniform head-to-tail connections with some head-to-head type connections in the structure.
  • These low branch ratio oligomers have high viscosity indices at least 15 to 20 units and typically 30-40 units higher than equivalent viscosity prior art oligomers, which regularly have higher branch ratios and correspondingly lower viscosity indices. These low branch oligomers maintain better or comparable pour points.
  • the branch ratios defined as the ratios of CH3 groups to CH2 groups in the lube oil are calculated from the weight fractions of methyl groups obtained by infrared methods, published in Analytical Chemistry , Vol. 25, No. 10, p. 1466 (1953).
  • supported Cr metal oxide in different oxidation states is known to polymerize alpha olefins from C3 to C20 (De 3427319 to H. L. Krauss and Journal of Catalysis 88, 424-430, 1984) using a catalyst prepared by CrO3 on silica.
  • the referenced disclosures teach that polymerization takes place at low temperature, usually less than 100 °C, to give adhesive polymers and that at high temperature, the catalyst promotes isomerization, cracking and hydrogen transfer reactions.
  • the present inventions produce low molecular weight oligomeric products under reaction conditions and using catalysts which minimize side reactions such as 1-olefin isomerization, cracking, hydrogen transfer and aromatization.
  • the reaction of the present invention is carried out at a temperature higher (90-250 oC) than the temperature suitable to produce high molecular weight polyalpha-olefins.
  • the catalysts used in the present invention do not cause a significant amount of side reactions even at high temperature when oligomeric, low molecular weight fluids are produced.
  • the catalysts for this invention thus minimize all side reactions but oligomerize alpha olefins to give low molecular weight polymers with high efficiency.
  • chromium oxides especially chromia with average +3 oxidation states, either pure or supported, catalyze double bond isomerization, dehydrogenation, cracking, etc.
  • the catalyst of the present invention is rich in Cr(II) supported on silica, which is more active to catalyze alpha-olefin oligomerization at high reaction temperature without causing significant amounts of isomerization, cracking or hydrogenation reactions, etc.
  • catalysts as prepared in the cited references can be richer in Cr (III). They catalyze alpha-olefin polymerization at low reaction temperature to produce high molecular weight polymers.
  • undesirable isomerization, cracking and hydrogenation reaction takes place at higher temperatures.
  • high temperatures are needed in this invention to produce lubricant products.
  • supported Cr catalysts rich in Cr(III) or higher oxidation states catalyze 1-butene isomerization with 103 higher activity than polymerization of 1-butene.
  • the quality of the catalyst, method of preparation, treatments and reaction conditions are critical to the catalyst performance and composition of the product produced and distinguish the present invention over the prior art.
  • the oligomers of 1-olefins prepared in this invention usually have much lower molecular weights than the polymers produced in cited reference which are semi-solids, with very high molecular weights. These high polymers are not suitable as lubricant basestocks and usually have no detectable amount of dimer or trimmer (C10-C30) components form synthesis. Such high polymers also have very low unsaturations. However, products in this invention are free-flowing liquids at room temperature, suitable for lube basestock, containing significant amount of dimer or trimer and have high unsaturations.
  • the temperature is then set at 600°C with dry air purging for 16 hours. At this time the catalyst is cooled down under N2 to a temperature of 300°C. Then a stream of pure CO (99.99% from Matheson) is introduced for one hour. Finally, the catalyst is cooled down to room temperature under N2 and ready for use.
  • Example 1 The catalyst prepared in Example 1 (3.2 g ) is packed in a 3/8" (0.95 cm) stainless steel tubular reactor inside an N2 blanketed dry box. The reactor under N2 atmosphere is then heated to 150°C by a single-zone Lindberg furnace. Pre-purified 1-hexene is pumped into the reactor at 965 kPa (140 psi) and 20 ml/hr. The liquid effluent is collected and stripped of the unreacted starting material and the low boiling material at 6.7 kPa (0.05 mm Hg). The residual clear, colorless liquid has viscosities and VI's suitable as a lubricant base stock.
  • Example 2 Similar to Example 2, a fresh catalyst sample is charged into the reactor and 1-hexene is pumped to the reactor at 101 kPa (1 atm) and 10 ml per hour. As shown below, a lube of high viscosities and high VI's is obtained. These runs show that at different reaction conditions, a lube product of high viscosities can be obtained.
  • a commercial chrome/silica catalyst which contains 1% Cr on a large-pore volume synthetic silica gel is used.
  • the catalyst is first calcined with air at 800°C for 16 hours and reduced with CO at 300°C for 1.5 hours. Then 3.5 g of the catalyst is packed into a tubular reactor and heated to 100°C under the N2 atmosphere. 1-Hexene is pumped through at 28 ml per hour at 101 kPa (1 atmosphere). The products are collected and analyzed as follows:
  • Example 4 purified 1-decene is pumped through the reactor at 1830 kPa to 2310 kPa (250 to 320 psi). The product is collected periodically and stripped of light products boiling points below 343°C (650°F). High quality lubes with high VI are obtained (see following table). Reaction Temp.°C WHSV g/g/hr Lube Product Properties V at 40°C (mm2/s) V at 100°C (mm2/s) VI 120 2.5 1555.4 157.6 217 135 0.6 389.4 53.0 202 150 1.2 266.8 36.2 185 166 0.6 67.7 12.3 181 197 0.5 21.6 5.1 172
  • the 1-decene oligomers as described below were synthesized by reacting purified 1-decene with an activated chromium on silica catalyst.
  • the activated catalyst was prepared by calcining chromium acetate (1 or 3% Cr) on silica gel at 500-800°C for 16 hours, followed by treating the catalyst with CO at 300-350°C for 1 hour.
  • 1-Decene was mixed with the activated catalyst and heated to reaction temperature for 16-21 hours. The catalyst was then removed and the viscous product was distilled to remove low boiling components at 200°C/13.3 kPa(0.1 mmHg).
  • the examples prepared in accordance with this invention have branch ratios of 0.14 to 0.16, providing lube oils of excellent quality which have a wide range of viscosities from 3 to 483.1 mm2/s at 100°C with viscosity indices of 130 to 280.
  • a commercial Cr on silica catalyst which contains 1% Cr on a large pore volume synthetic silica gel is used.
  • the catalyst is first calcined with air at 700°C for 16 hours and reduced with CO at 350°C for one to two hours.
  • 1.0 part by weight of the activated catalyst is added to 1-decene of 200 parts by weight in a suitable reactor and heated to 185°C.
  • 1-Decene is continuously fed to the reactor at 2-3.5 parts/minute and 0.5 parts by weight of catalyst is added for every 100 parts of 1-decene feed.
  • the slurry is stirred for 8 hours.
  • the catalyst is filtered and light product boiled below 150°C @ 0.1mm Hg is stripped.
  • the residual product is hydrogenated with a Ni on Kieselguhr catalyst at 200°C.
  • the finished product has a viscosity at 100°C of 18.5 mm2/s(cs), VI of 165 and pour point of -55°C.
  • reaction temperature is 125°C.
  • the finished product has a viscosity at 100°C of 145 mm2/s(cs), VI of 214, pour point of -40°C.
  • Example 16 is repeated except reaction temperature is 100°C.
  • the finished product has a viscosity at 100°C of 298 mm2/s, VI of 246 and pour point of -32°C.
  • the final lube products in Example 16 to 18 contain the following amounts of dimer and trimer and isomeric distribution (distr.).
  • the molecular weights and molecular weight distributions are analyzed by a high pressure liquid chromatography, composed of a Constametric II high pressure, dual piston pump from Milton Roy Co. and a Tracor 945 LC detector.
  • the system pressure is 4600 kPa (650 psi) and THF solvent (HPLC grade) deliver rate is 1 ml per minute.
  • the detector block temperature is set at 145 °C. ml of sample, prepared by dissolving 1 gram PAO sample in ml THF solvent, is injected into the chromatograph.
  • the sample is eluted over the following columns in series,all from Waters Associates: Utrastyragel 105 A, P/N 10574, Utrastyragel 104 A, P/N 10573, Utrastyragel 103 A, P/N 10572, Utrastyragel 500 A, P/N 10571.
  • the molecular weights are calibrated against commercially available PAO from Mobil Chemical Co, Mobil SHF-61 and SHF-81 and SHF-401.
  • Examples 16 17 18 V @100 °C,mm2/s(cs) 18.5 145 298 VI 165 214 246 number-averaged molecular weights, MW n 1670 2062 5990 weight-averaged molecular weights, MW w 2420 4411 13290 molecular weight distribution, MWD 1.45 2.14 2.22
  • HVI-PAO product with viscosity as low as 3 mm2/s (cs) and as high as 500 mm2/s (cs), with VI between 130 and 280, can be produced.
  • Ethene can be employed as a starting material for conversion to higher C6-C20 alpha olefins by conventional catalytic procedure, for instance by contacting ethene with a Ni catalyst at 80-120°C and about 7000 kPa (1000 psi) using commercial synthesis methods described in Chem System Process Evaluation/Research Planning Report - Alpha-Olefins, report number 82-4.
  • the intermediate product alpha olefin has a wide distribution range from C6 to C20 carbons.
  • the complete range of alpha olefins from growth reaction, or partial range such as C6 to C14, can be used to produce a lube of high yields and high viscosity indices.
  • the oligomers after hydrogenation have low pour points.
  • a range of alpha olefins from ethylene growth reactions and metathesis processes can be used to produce high quality lube by the present process, thus rendering the process cheaper and the feedstock flexible than using pure single monomer.
  • the standard 1-decene oligomerization synthesis procedure employed above is repeated at 125°C using different Group VIB metal species, tungsten or molydenum.
  • the W/Mo treated porous substrate is reduced with CO at 460°C to provide 1 wt. % metal in reduced oxide state.
  • Molybdenum catalyst gives a 1% yield of a viscous liquid. Tungsten gives C20 dimer only.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (24)

  1. Flüssige Schmiermittelzusammensetzung, die C₃₀-C₁₃₀₀-Kohlenwasserstoffe umfaßt, wobei die Zusammensetzung ein Verzweigungsverhältnis zwischen 0,1 und 0,16, ein gewichtsmittleres Molekulargewicht zwischen 300 und 45000, ein zahlenmittleres Molarkulargewicht zwischen 300 und 18000, eine Molekulargewichtsverteilung zwischen 1 und 5 und einen Fließpunkt unterhalb von -15°C aufweist.
  2. Zusammensetzung nach Anspruch 1, worin die Kohlenwasserstoffe C₃₀-C₁₀₀₀-Kohlenwasserstoffe und eine Molekulargewichtsverteilung von 1,05 bis 2,5 umfassen.
  3. Zusammensetzung nach Anspruch 1, worin die Kohlenwasserstoffe Alkane oder Alkene umfassen.
  4. Zusammensetzung nach Anspruch 1, die einen Viskositätsindex von mehr als 130 und bei 100°C eine Viskosität zwischen 3 mm²/s und 750 mm²/s aufweist.
  5. Zusammensetzung nach Anspruch 1, mit einer C₃₀-Fraktion mit einem Viskositätsindex von mehr als 130 und einem Fließpunkt unterhalb von -45°C.
  6. Zusammensetzung nach Anspruch 1, worin die Zusammensetzung den Polymerrückstand der 1-Alkene, der aus linearen C₆-C₂₀ 1-Alkenen stammt, umfaßt.
  7. Zusammensetzung nach Anspruch 6, worin die 1-Alkene C₈-C₁₂ Alkene umfassen.
  8. Zusammensetzung nach Anspruch 6, worin der Polymerrückstand den hydrierten Polymerrückstand der 1-Alkene umfaßt.
  9. Zusammensetzung nach Anspruch 6, worin der Polymerrückstand Poly-1-Decen umfaßt.
  10. Zusammensetzung nach Anspruch 9, worin der Polymerrückstand aus 1-Decen ein Molekulargewicht von etwa 422 aufweist.
  11. Zusammensetzung nach Anspruch 10 mit einem Viskositätsindex von etwa 134 und einem Fließpunkt von weniger als -45°C.
  12. Flüssige Schmiermittel-Kohlenwasserstoffzusammensetzung mit der wiederkehrenden Polymerstruktur
    Figure imgb0015
     worin n 3 bis 17 ist und x 5 bis 500 ist.
  13. Zusammensetzung nach Anspruch 12, worin n sieben und das durchschnittliche x mindestens fünfzehn beträgt.
  14. Zusammensetzung nach Anspruch 12 mit einem Viskositätsindex von mehr als 30 und einem Fließpunkt von weniger als -15°C.
  15. Kohlenwasserstoffzusammensetzungen nach einem der vorangegangenen Ansprüche, worin die C₃₀-C₁₃₀₀-Kohlenwasserstoffe 9-Methyl-11-octylheneicosan und 11-Octyldocosan umfassen.
  16. Zusammensetzung nach Anspruch 15, worin das Molverhältnis von 9-Methyl-11-Octylheneicosan:11-Octyldocosan zwischen 1:10 und 10:1 beträgt.
  17. Zusammensetzung nach Anspruch 16, worin das Molverhältnis vorzugsweise 1:2 bis 2:1 beträgt.
  18. Zusammensetzung nach Anspruch 15, worin das 11-Octyldocosan die Struktur
    Figure imgb0016
     aufweist.
  19. Verfahren zur Herstellung flüssiger Kohlenwasserstoffe, die als Schmiermittelgrundmaterialien geeignet sind, aus Alphaolefinen, die 6 bis 20 Kohlenstoffatome enthalten, oder aus Gemischen solcher Olefine, das umfaßt: Kontaktierung der Olefine unter Oligomerisierungsbedingungen bei einer Reaktionstemperatur von etwa 90 bis 250°C mit einem Chromkatalysator an einem porösen Träger, wobei dieser Katalysator durch Oxidation bei einer Temperatur von 200°C bis 900°C in Gegenwart eines oxidierenden Gases und dann mit einem Reduktionsmittel bei einer Temperatur und für eine zur Reduktion des Katalysators in eine niedrige Wertigkeitsstufe ausreichende Zeit behandelt wurde, um eine oligomere, flüssige Schmiermittelzusammensetzung zu erhalten, die C₃₀-C₁₃₀₀-Kohlenwasserstoffe umfaßt, wobei die Zusammensetzung ein Verzweigungsverhältnis zwischen 0,1 und 0,16, ein gewichtsmittleres Molekulargewicht zwischen 300 und 45000, ein zahlenmittleres Molekulargewicht zwischen 300 und 18000, eine Molekulargewichtsverteilung zwischen 1 und 5 und einen Fließpunkt unterhalb von -15°C aufweist.
  20. Verfahren nach Anspruch 19, worin das Reduktionsmittel CO umfaßt, die Oligomerisierungstemperatur etwa 100-180°C beträgt und die Ausbeute an C₃₀-Oligomer für ein Produkt mit einer Viskosität von mindestens 15 mm²/s bei 100°C mindestens 85 Gew.-% beträgt.
  21. Verfahren nach Anspruch 19 oder 20, worin der Träger poröses Siliciumdioxid umfaßt.
  22. Verfahren nach Anspruch 19, 20 oder 21, worin das Olefin im wesentlichen aus 1-Octen, 1-Decen, 1-Dodecen, 1-Tetradecen oder aus Gemischen daraus besteht.
  23. Verfahren nach Anspruch 19, 20 oder 21, worin der Katalysator nach der Reduktion keiner weiteren Oxidation unterworfen wird.
  24. Verfahren nach Anspruch 19, 20 oder 21, worin das Olefin 1-Decen umfaßt und das Oligomer einen VI von 181 oder größer und ein Verzweigungsverhältnis von 0,14 bis 0,16 aufweist.
EP89905983A 1988-06-23 1989-04-28 Olefinoligomere mit schmierungseigenschaften und verfahren zu ihrer herstellung Expired - Lifetime EP0422019B1 (de)

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US07/210,434 US4827073A (en) 1988-01-22 1988-06-23 Process for manufacturing olefinic oligomers having lubricating properties
US07/210,435 US4827064A (en) 1986-12-24 1988-06-23 High viscosity index synthetic lubricant compositions
US210435 1988-06-23
US210434 2000-06-08

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US4962249A (en) * 1988-06-23 1990-10-09 Mobil Oil Corporation High VI lubricants from lower alkene oligomers
ATE113649T1 (de) * 1989-04-25 1994-11-15 Mobil Oil Corp Schmiermitteladditive.
US4990709A (en) * 1989-04-28 1991-02-05 Mobil Oil Corporation C2-C5 olefin oligomerization by reduced chromium catalysis
US4967032A (en) * 1989-09-05 1990-10-30 Mobil Oil Corporation Process for improving thermal stability of synthetic lubes
DE4136617C2 (de) * 1991-11-07 1997-08-14 Henkel Kgaa Füllmasse und deren Verwendung
US5902849A (en) * 1991-11-07 1999-05-11 Henkel Kommanditgesellschaft Auf Aktien Filling compound
EP0613873A3 (de) * 1993-02-23 1995-02-01 Shell Int Research Verfahren zur Oligomenisierung.
US6090989A (en) * 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
US6150574A (en) * 1999-05-06 2000-11-21 Mobil Oil Corporation Trialkymethane mixtures as synthetic lubricants
US8399390B2 (en) * 2005-06-29 2013-03-19 Exxonmobil Chemical Patents Inc. HVI-PAO in industrial lubricant and grease compositions
US7943807B2 (en) 2008-02-06 2011-05-17 Chemtura Corporation Controlling branch level and viscosity of polyalphaolefins with propene addition
JP5357605B2 (ja) * 2009-04-02 2013-12-04 出光興産株式会社 α−オレフィン重合体の製造方法及び潤滑油
NZ597113A (en) 2009-06-16 2014-03-28 Chevron Phillips Chemical Co Oligomerization of alpha olefins using metallocene-ssa catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends
FR3021664B1 (fr) * 2014-05-30 2020-12-04 Total Marketing Services Polyolefines lubrifiantes de basse viscosite

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EP0422019A1 (de) 1991-04-17
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CA1325020C (en) 1993-12-07
AU3563289A (en) 1990-01-12
MY105050A (en) 1994-07-30
FI96775C (fi) 1996-08-26
CZ277758B6 (en) 1993-04-14
AU637974B2 (en) 1993-06-17
JP2913506B2 (ja) 1999-06-28
ES2059829T3 (es) 1994-11-16
FI96775B (fi) 1996-05-15
SK277757B6 (en) 1994-12-07
DE68911142T2 (de) 1994-03-31
ES2011734A6 (es) 1990-02-01

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