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WO1989012662A1 - Oligomeres olefiniques ayant des proprietes lubrifiantes et leur procede de production - Google Patents

Oligomeres olefiniques ayant des proprietes lubrifiantes et leur procede de production Download PDF

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Publication number
WO1989012662A1
WO1989012662A1 PCT/US1989/001843 US8901843W WO8912662A1 WO 1989012662 A1 WO1989012662 A1 WO 1989012662A1 US 8901843 W US8901843 W US 8901843W WO 8912662 A1 WO8912662 A1 WO 8912662A1
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Prior art keywords
composition
catalyst
molecular weight
lubricant
pour point
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PCT/US1989/001843
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English (en)
Inventor
Margaret May-Som Wu
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Mobil Oil Corporation
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Priority claimed from US07/210,435 external-priority patent/US4827064A/en
Priority claimed from US07/210,434 external-priority patent/US4827073A/en
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to AT89905983T priority Critical patent/ATE97946T1/de
Priority to DE89905983T priority patent/DE68911142T2/de
Publication of WO1989012662A1 publication Critical patent/WO1989012662A1/fr
Priority to FI906317A priority patent/FI96775C/fi

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Classifications

    • 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 compos itions 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 .
  • the oligomerization of 1-decene for example, to lubricant oligomers in the C,Q and C.Q range can result in a very large number of structural isomers. Henze and
  • 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 Che istrv, 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 synthes ized from 1-alkenes .
  • oligomers prepared from 1-decene by either cationic polymerization or Ziegler catalyst polymerization have branch ratios of greater than 0.20.
  • Other explanations suggest isomerization of the olefinic group in the one position to produce an internal oiefin as the cause for branching .
  • U.S. Patent 4 , 282 , 392 to Cupples et al discloses an alpha-olefin oligomer synthetic lubri cant having an improved viscos ity-volatil ity relationship and containing a high proportion of tetramer and pentamer via a hydrogenation process that effects skeletal rearrangement and isomeric compos ition .
  • the compos ition claimed is a trimer to tetramer ratio no higher than one to one. The branch ratio is not disclosed .
  • oiefin oligomers and more particularly PAO oligomers have been produced by methods in whic double bond isomerization of the starting 1-olefin occurrs easily. As a result, the oiefin oligomers have more short side branches. These side branches degrade their lubricating properties .
  • Liquid hydrocarbon lubricant compos itions have been obtained from Cg-C ⁇ Q 1-alkene oligomerization that exhibit surprisingly high viscos ity index (VT) while, equally surprisingly, exhibit very low pour points.
  • the compositions comprise
  • compos ition has been found to exhibit superior lubricant properties either alone or in a mixture with 9-methyl,ll-octylhenei cosane.
  • the mixture has a viscosity index of greater than 130, preferably from 130 to 280, while maintaining a pour point less than -15°C.
  • compos itions are representative of the instant invention comprising C,QH 62 alkanes having a branch ratio, or CH,/CH 2 ratio, of less than 0.19, preferably 0.10 to 0.16.
  • compositions of the invention ref erred to herein as polyalpha -oiefin or HVI-PAO, conferring upon the compos itions especially high viscos ity indices in comparison to commercially available polyalpha-olefin (PAO) synthetic lubricants .
  • Unique lubricant oligomers of the instant invention an also be made in a wide range of molecular weights and viscosities comprising C, Q to C I QQQ -hydrocarbons having a branch ratio of less than 0.19 and molecular weight distribution of about 1.05 to 2.5.
  • the oligomers can be mixed wi th conventional mineral oils or greases of other properties to provide compos itions also possessing outstanding lubricant properties .
  • Compos itions of the present invention 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 present invention provides a process for producing liquid oligomers of olefins , such as 1-decene, with branch ratios below 0. 19 and having higher viscosity indi ces than oligomers with higher branch ratios .
  • olefins such as 1-decene
  • branch ratios below 0. 19
  • ol igomers with low branch ratios can be used as basestocks for many lubri cants or greases with an improved viscos ity-temperature relationship, oxidative stabil ity , volatil ity , 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. More particularly, 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 cons ists essentially of substantially non-iso erized olefins .
  • alpha olefins such as 1-decene, and wherein a major proporti on 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.
  • Figure 1 is a comparison of PAO and HVI-PAO syntheses .
  • Figure 2 compares VI for PAO and HVI-PAO
  • 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 5cs HVI-PAO from
  • Figure 6 shows C- 13 NMR spectra of 50cs HVI-PAO from 1-decene.
  • Figure 7 shows C-13 NMR spectra of 145cs HVI-PAO from 1-decene.
  • Figure 8 shows the gas chro atograph of HVI-PAO 1-decene t rimer.
  • 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-olef ins .
  • 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. — 1-
  • HVI-PAO high viscos ity index polyalphaolefins
  • PAO polyalphaolefins
  • Conventional PAO, on the other hand promoted by BF, or A1C13 forms a carbonium ion which, in turn, promotes isomerization of the olefini c bond and the formation of multiple isomers.
  • the HVI-PAO produced in the present invention has a structure with a CH-./CHH.- ratio ⁇ 0.19 compared to a ratio of > 0.20 for PAO.
  • Figure 2 compares the viscos ity index versus viscosity relationship for HVI -PAO and PAO lubricants , showing that HVI-PAO is distinctly superior to PAO at all viscos ities tested.
  • HVI-PAO oligomers as shown by branch ratio that results in improved viscosity index (VI) , they show pour points superior to PAO.
  • oligomers of regular structure containing fewer isomers would be expected to have higher sol idification temperatures and higher pour points , reducing their util ity as lubricants . But , surprisingly , such is not the case for HVI-PAO of the present invention .
  • Figure 2 and 3 illustrate superiori ty of HVI-PAO in terms of both pour point and VI.
  • molecular weights range from C- to C, ,QQ and viscosity up to 750 mm 2 /s(cs ) at 100°C, with a preferred range of C, Q to C- fi00 and a viscos ity of up to 500 mm /s(cs) at 100°C, preferably between 3 and 750 mm /s .
  • Molecular weight distributions defined as the ratio of weight average molecular weight to number average molecular weight , range from 1.00 to 5 , with a preferred range of 1.01 to 3 and a more preferred MWD of about 1.05 to 2.5.
  • HVI-PAO of the present invention has been found to have a higher proportion of higher molecular weight polymer molecules in the product.
  • novel oligomer compos itions disclosed herein have been examined to define their unique structure beyond the important characteristics of branch ratio and molecular weight already noted.
  • 1-hexene HVI-PAO oligomers of the present invention have been shown to have a very uniform linear C . branch and contain
  • the backbone structures have some head-to-head connection, indicative of the following structure as confirmed by NMR: ._ ⁇ _.-
  • NMR poly(l-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
  • Table A presents the NMR data for
  • novel oligomers have the following regular head-to-tail structure where n can be 3 to 17 : -CGH 2 -(H) ⁇ -
  • trimer of 1-decene HVI-PAO oligomer is separated from
  • the trimer is hydrogenated at 235 °C and 4200 kPa H 2 with
  • 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 surpris ingly simpler and useful dimer compared to the dimer produced by 1-alkene oligomerization with BF, or A1C1, as commercially practi ced.
  • i t has been found that a significant proportion of unhydrogenated dimerized 1-alkene has a vinylidenyl structure as follows :
  • R, and R- are alkyl groups representing the residue from the head-to-tail addition of 1-alkene molecules .
  • 1-decene dimer of the invention has been found to contain only three major components, as determined by GC. Based on C NMR analysis , 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-ei cosane and 9-methylnonacosane .
  • Olefins suitable for use as starting material in the inventi on include those olefins containing from 2 to about 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
  • olef in-containing refinery feedstocks or effluents are also suitable for use.
  • 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 less than 0.19 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.
  • the support material usually has high surface area and large pore volumes with average pore size of 40 to 350 x .
  • 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
  • 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 , H 2 , NH-, , H 2 S, CS 7 , CH-.SCH-, , CH,SSCH, , metal alkyl containing compounds such as R 3 A1 , R,B,R 2 Mg , RLi , R_,Zn, where R is alkyl , alkoxy, aryl and the like. Preferred are CO or H 2 or metal alkyl containing compounds .
  • the Group VIB metal may be applied to the substrate in reduced form, such as CrI I compounds.
  • the resultant catalyst is very active for oligomerizing olefins at a temperature range from below room temperature to about 250°C, preferably
  • WHSV weight hourly space velocity
  • 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.
  • the product oligomers have a very wide range of viscosities with high viscos ity 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 0 maintain better or comparable pour points .
  • branch ratios defined as the ratios of CH, groups to CH 2 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) . 5
  • Branch ratio wt fraction of methyl group
  • supported Cr metal oxide in different oxidation states is known to polymerize alpha olefins from 0 C 3 to C (De 3427319 to H. L. Krauss and Journal of Catalysis
  • 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
  • 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 aromati ⁇ ation.
  • 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-olef ins .
  • 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(I I) supported on silica, which is more active to catalyze alpha-olefin oligomerization at high reaction temperature without caus ing significant amounts of isomerization , cracking or hydrogenation reacti ons , etc .
  • catalysts as prepared in the ci ted references can be richer in Cr (I II) . They catalyze alpha-olefin polymerization at low reaction temperature to produce high molecular weight polymers .
  • references teach, undes irable isomerization, cracking and hydrogenation reaction takes place at higher temperatures . In contrast , high temperatures are needed in this invention to produce lubricant products.
  • the prior art also teaches that supported Cr catalysts rich in Cr(III). or higher
  • 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
  • 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.
  • Example 1 The catalyst prepared in Example 1 (3.2 g ) is packed in a 3/8" stainless steel tubular reactor inside an N 2 blanketed dry box. The reactor under N 2 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 viscos ities and VI ' s suitable as a lubricant base stock.
  • 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 N 2 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 5 As in 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 can be carried out in a batch operation.
  • 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 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) .
  • HVI-PAO HVI-PAO are summarized below:
  • oligomers of alpha-olefins as 1-decene, with branch ratios lower than 0.19, preferably from 0.13 to 0.18, have higher VI and are better lubricants .
  • 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 cs 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
  • the finished product has a viscosity at 100 °C of 145 2 ran /s(cs), VI of 214, pour point of -40°C.
  • Example 16 is repeated except reaction temperature is
  • Example 16 to 18 contain the following amounts of dimer and trimer and isomeric distribution
  • 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 chroma tograph.
  • the sample is eluted over the following columns in series, all from Waters Associates : Utrastyragel 10 5 A, P/N 10574 , Utrastyragel 10 4 A, P/N 10573 , Utrastyragel 10 3 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.
  • HVT-PAO product with viscosity as low as 3 mm 2 /s (cs) and as high as 500 mm 2 /s (cs) , with VI between 130 and 280 , can be produced.
  • Ethene can be employed as a starting material for conversion to higher C 6 -C 2Q 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
  • the intermediate product alpha oiefin has a wide distribution range from Cg to C 2Q carbons.
  • C 14 can be used to produce a lube of high yields and high viscosity indices .
  • the oligomers after hydrogenation have low pour points.
  • Example 19 An alpha oiefin growth reaction mixture, as described above, containing C 6 ⁇ C 8 ⁇ c ⁇ o" c i2" C 14 ⁇ C 16 ⁇ C 18" C 20 of equal molar concentration is reacted with 2 wt. % activated Cr/Si0 2 catalyst at 130°C and under nitrogen atmosphere. After 225 minutes reaction time, the catalyst is filtered and the reaction mixture distilled to remove light fraction which boils below 120°C/0.1 mm-Iig. The residual lube yield is 95% and has V- I QO O Q 67.07 cS and VI 195.
  • Example 20 An equimolar C,. -C- > Q alpha oiefin mixture as described above is fed continuously over activated Cr/Si0 2 catalyst packed in a tubular reactor. The results are summarized below.
  • 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.
  • Example 22 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 C 20 dimer only.
  • the use of supported Group VIB oxides as a catalyst to oligomerize olefins to produce low branch ratio lube products with low pour points was heretofore unknown.

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  • 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)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Des compositions lubrifiantes nouvelles comprenant des polyalpha-oléfines ont un indice de viscosité élevé et un point d'écoulement réduit. Ces compositions se caractérisent par le fait d'avoir une structure moléculaire uniforme avec un faible taux de ramifications. Une composition lubrifiante liquide comprend des hydrocarbures C30-C1300 et un taux de ramifications inférieur à 0,19, un poids moléculaire moyen pondéré compris entre 300 et 45.000, un poids moléculaire moyen numérique compris entre 300 et 18.000, une distribution de poids moléculaires comprise entre 1 et 5 et un point d'écoulement inférieur à -15°C. L'invention concerne un 1-décène trimère comprenant du 9-méthyle, du 11-octylhénéicosane et du 11-octyldocosane. On produit ces compositions lubrifiantes en mettant l'alpha oléfine en contact avec un catalyseur solide réduit de support du groupe VIB (par exemple du chrome) dans des conditions d'oligomérisation à une température comprise entre 40 et 250 °C environ afin de produire un hydrocarbure lubrifiant liquide. Le produit hydrocarbure hydrogéné dans la classe des lubrifiants a un indice de viscosité compris entre 130 et 280 environ et une viscosité qui peut s'élever jusqu'à 750 mm2/s(cs). Ce procédé est particulièrement utile lorsque l'alpha oléfine de base comprend essentiellement un hydrocarbure oléfinique ayant entre 8 et 14 atomes de carbone ou des mélanges de ceux-ci, lorsque les conditions de mise en oeuvre du procédé comprennent une température de réaction comprise entre 100 et 180 °C environ, et lorsque le catalyseur de support comprend de la silice poreuse inerte.
PCT/US1989/001843 1988-06-23 1989-04-28 Oligomeres olefiniques ayant des proprietes lubrifiantes et leur procede de production WO1989012662A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT89905983T ATE97946T1 (de) 1988-06-23 1989-04-28 Olefinoligomere mit schmierungseigenschaften und verfahren zu ihrer herstellung.
DE89905983T DE68911142T2 (de) 1988-06-23 1989-04-28 Olefinoligomere mit schmierungseigenschaften und verfahren zu ihrer herstellung.
FI906317A FI96775C (fi) 1988-06-23 1990-12-20 Voiteluainekoostumus ja menetelmä sen valmistamiseksi

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US210,435 1988-06-23
US07/210,435 US4827064A (en) 1986-12-24 1988-06-23 High viscosity index synthetic lubricant compositions
US210,434 1988-06-23
US07/210,434 US4827073A (en) 1988-01-22 1988-06-23 Process for manufacturing olefinic oligomers having lubricating properties

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JP (1) JP2913506B2 (fr)
AU (1) AU637974B2 (fr)
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CZ (1) CZ277758B6 (fr)
DE (1) DE68911142T2 (fr)
ES (2) ES2059829T3 (fr)
FI (1) FI96775C (fr)
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416874A1 (fr) * 1989-09-05 1991-03-13 Mobil Oil Corporation Procédé d'amélioration de la stabilité thermique d'huiles lubrifiantes synthétiques
EP0442656A1 (fr) * 1990-02-15 1991-08-21 Mobil Oil Corporation Lubrifiants à haut indice de viscosité à partir d'oligomères d'oléfines inférieures
EP0541007A1 (fr) * 1991-11-07 1993-05-12 Henkel KGaA Charge de remplissage
EP0613873A2 (fr) * 1993-02-23 1994-09-07 Shell Internationale Researchmaatschappij B.V. Procédé d'oligomérisation
US5902849A (en) * 1991-11-07 1999-05-11 Henkel Kommanditgesellschaft Auf Aktien Filling compound
WO2015181358A1 (fr) 2014-05-30 2015-12-03 Total Marketing Services Polyoléfines lubrifiantes de basse viscosité
US9334203B2 (en) 2009-06-16 2016-05-10 Chevron Phillips Chemical Company Lp Oligomerization of alpha olefins using metallocene-SSA catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990012857A1 (fr) * 1989-04-25 1990-11-01 Mobil Oil Corporation Nouveaux additifs lubrifiants
US4990709A (en) * 1989-04-28 1991-02-05 Mobil Oil Corporation C2-C5 olefin oligomerization by reduced chromium catalysis
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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3206523A (en) * 1964-07-14 1965-09-14 Sun Oil Co Preparation of synthetic lubricating oil
EP0000748A1 (fr) * 1977-08-03 1979-02-21 Kurt Schulze Procédé de préparation de polymères d'éthylène
US4282392A (en) * 1976-10-28 1981-08-04 Gulf Research & Development Company Alpha-olefin oligomer synthetic lubricant
EP0034303A2 (fr) * 1980-02-06 1981-08-26 Phillips Petroleum Company Procédé pour la fabrication d'un catalyseur de polymérisation d'oléfines, catalyseur de polymérisation sur support et procédé de polymérisation
US4362654A (en) * 1981-05-14 1982-12-07 The Dow Chemical Company Chromium-containing catalysts for polymerizing olefins
DE3427319A1 (de) * 1984-07-25 1986-01-30 Hans-Ludwig Prof. Dipl.-Chem. Dr. 8600 Bamberg Krauss Verfahren zur herstellung von ueberwiegend ataktischen polymeren aus olefinen
US4587368A (en) * 1983-12-27 1986-05-06 Burmah-Castrol, Inc. Process for producing lubricant material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4613712A (en) * 1984-12-31 1986-09-23 Mobil Oil Corporation Alpha-olefin polymers as lubricant viscosity properties improvers

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3206523A (en) * 1964-07-14 1965-09-14 Sun Oil Co Preparation of synthetic lubricating oil
US4282392A (en) * 1976-10-28 1981-08-04 Gulf Research & Development Company Alpha-olefin oligomer synthetic lubricant
EP0000748A1 (fr) * 1977-08-03 1979-02-21 Kurt Schulze Procédé de préparation de polymères d'éthylène
EP0034303A2 (fr) * 1980-02-06 1981-08-26 Phillips Petroleum Company Procédé pour la fabrication d'un catalyseur de polymérisation d'oléfines, catalyseur de polymérisation sur support et procédé de polymérisation
US4362654A (en) * 1981-05-14 1982-12-07 The Dow Chemical Company Chromium-containing catalysts for polymerizing olefins
US4587368A (en) * 1983-12-27 1986-05-06 Burmah-Castrol, Inc. Process for producing lubricant material
DE3427319A1 (de) * 1984-07-25 1986-01-30 Hans-Ludwig Prof. Dipl.-Chem. Dr. 8600 Bamberg Krauss Verfahren zur herstellung von ueberwiegend ataktischen polymeren aus olefinen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
No further relevant documents have been disclosed. *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU634808B2 (en) * 1989-09-05 1993-03-04 Mobil Oil Corporation Process for improving thermal stability of synthetic lubes
EP0416874A1 (fr) * 1989-09-05 1991-03-13 Mobil Oil Corporation Procédé d'amélioration de la stabilité thermique d'huiles lubrifiantes synthétiques
EP0442656A1 (fr) * 1990-02-15 1991-08-21 Mobil Oil Corporation Lubrifiants à haut indice de viscosité à partir d'oligomères d'oléfines inférieures
US6258885B1 (en) 1991-11-04 2001-07-10 Henkel Kommanditgesellschaft Auf Aktien Filling compound
EP0541007A1 (fr) * 1991-11-07 1993-05-12 Henkel KGaA Charge de remplissage
EP0739974A3 (fr) * 1991-11-07 1996-11-20 Henkel Kommanditgesellschaft auf Aktien Charge de remplissage
US5902849A (en) * 1991-11-07 1999-05-11 Henkel Kommanditgesellschaft Auf Aktien Filling compound
WO1993009208A1 (fr) * 1991-11-07 1993-05-13 Henkel Kommanditgesellschaft Auf Aktien Matiere de remplissage
EP0613873A2 (fr) * 1993-02-23 1994-09-07 Shell Internationale Researchmaatschappij B.V. Procédé d'oligomérisation
EP0613873A3 (fr) * 1993-02-23 1995-02-01 Shell Int Research Procédé d'oligomérisation.
US9334203B2 (en) 2009-06-16 2016-05-10 Chevron Phillips Chemical Company Lp Oligomerization of alpha olefins using metallocene-SSA catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends
US9745230B2 (en) 2009-06-16 2017-08-29 Chevron Phillips Chemical Company Lp Oligomerization of alpha olefins using metallocene-SSA catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends
WO2015181358A1 (fr) 2014-05-30 2015-12-03 Total Marketing Services Polyoléfines lubrifiantes de basse viscosité
FR3021664A1 (fr) * 2014-05-30 2015-12-04 Total Marketing Services Polyolefines lubrifiantes de basse viscosite
CN106414680A (zh) * 2014-05-30 2017-02-15 道达尔销售服务公司 低粘度润滑聚烯烃

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SK277757B6 (en) 1994-12-07
CS8903069A2 (en) 1991-10-15
EP0422019B1 (fr) 1993-12-01
EP0422019A1 (fr) 1991-04-17
AU3563289A (en) 1990-01-12
CA1325020C (fr) 1993-12-07
DE68911142T2 (de) 1994-03-31
FI96775B (fi) 1996-05-15
EP0422019A4 (fr) 1991-02-05
ES2059829T3 (es) 1994-11-16
CZ277758B6 (en) 1993-04-14
JPH03505887A (ja) 1991-12-19
MY105050A (en) 1994-07-30
JP2913506B2 (ja) 1999-06-28
AU637974B2 (en) 1993-06-17
FI906317A0 (fi) 1990-12-20
DE68911142D1 (de) 1994-01-13
FI96775C (fi) 1996-08-26
ES2011734A6 (es) 1990-02-01

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