JP2913506B2 - Olefinic oligomers having lubricity and process for producing the oligomers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel lubricant compositions, especially novel synthetic lubricant compositions made from alpha-olefins or 1-alkenes. The present invention relates to novel synthetic lubricant compositions from 1-alkenes which exhibit excellent viscosity index and other improved properties inherently useful in lubricating oils. The invention further relates to a method for preparing said lubricant composition.

Efforts to improve the performance of naturally occurring mineral oil-based lubricants through the synthesis of oligomeric hydrocarbon fluids have been an important research and development subject in the petroleum industry for at least the last 15 years, primarily based on the oligomerization of alpha-olefins or 1-alkenes. A number of superior polyalpha-olefin (PAO) synthetic lubricants have been introduced to the market relatively recently. In improving the properties of lubricants, the direction of industrial research efforts on synthetic lubricants has been to use useful viscosities over a wide range of temperatures, ie, improved viscosity index (VI), and to improve lubricity, thermal and oxidative stability and mineral oil. Intended for fluids with equal or better pour points. This new synthetic lubricant reduces friction and improves mechanical efficiency over the entire mechanical load from the worm gear to the towing vehicle and is superior to mineral oil lubricants over a wider range of operating conditions.

The chemical focus of synthetic lubricant research efforts has been on the polymerization of 1-alkenes. The relationship between the structure and properties of well-known high polymers, such as those found in various fields of polymer chemistry, is due to the effect of the synthesis of oligomers with structures that appear to be necessary for the 1-alkene to provide improved lubricant properties. It indicates that this is a research field. Studies on the polymerization of propane and vinyl monomers have well appreciated the mechanism of polymerization of 1-alkenes and their impact on polymer structure, and a powerful tool for targeting useful oligomerization methods and oligomer structures. give. By this means, the conventional C ₆ -C ₂₀
Oligomers of 1-alkenes have been produced, especially 1-alkenes.
Commercially useful synthetic lubricants have been produced from the oligomerization of decene, yielding distinctly superior lubricant products by either cationic polymerization or Ziegler-catalyzed polymerization.

Theoretically, for example, the oligomerization of 1-decene to a lubricant oligomer in the C ₃₀ -C ₄₀ range can result in a large number of structural isomers. In JACS 54,1538, Hentz and Pleia calculated 60 × 10 ¹² isomers for C ₃₀ -C ₄₀ .
The discovery of isomers and associated oligomerization methods that produce preferred, superior synthetic lubricants that meet the specific requirements of a wide range of temperature fluidity while maintaining a low pour point poses significant challenges for researchers in the field. providing. Brennan In
d.Eng.Chem.Prod.Res.Dev. 1980,19,2-6 Structure example comparable to a structure with good low-temperature fluidity such that the atomic concentration is very close to the center of the carbon atom chain As 1-decene trimer. It also describes an oligomerization process of oligomeric nature, ie a clear dependency on cationic polymerization or Ziegler type catalysts known and practiced in the art.

One property of the molecular structure of 1-alkene oligomers that has been found to correlate very well with the improved lubricity of commercial synthetic lubricants is the ratio of methyl to methylene groups in the oligomer. This ratio is called the branched ratio Analytical Chemi
Calculated from infrared data as described in “High-molecular-weight standard hydrocarbons” in stry. 25, No. 10.1466 (1953). It has been found that the viscosity index increases with low branching ratio. Heretofore, oligomeric lubricating fluids having a low branching ratio have not been synthesized from 1-alkenes. Oligomers made from 1-decene, for example by either cationic polymerization or Ziegler-catalyzed polymerization, have a branching ratio greater than 0.20. Shibukin's Ind.Eng.Chem, Prod.Re
s, Dev. 1980 , 19.15-19, describes an apparent control value of the branching ratio based on a cationic polymerization reaction mechanism that includes rearrangements that produce branching. Another explanation is that the cause of branching is 1
This suggests isomerization of the olefin group at position to produce an internal olefin. Excessive branching occurs in the field of 1-alkene oligomerization reactions for the production of synthetic lubricants, as practiced to date, whether by rearrangement, isomerization or another mechanism, particularly with respect to the viscosity index. Clearly, it limits the limits on the properties of the resulting lubricant.
Obviously, the increased branching increases the number of isomers in the oligomer mixture, and directs the composition to a structure that is different from the preferred structure in view of the above theoretical concepts.

U.S. Pat. No. 4,282,392 to Kutpres et al. Discloses an alpha-olefin having an improved viscosity-volatility relationship and containing a high proportion of tetramers and pentamers by a hydrogenation operation resulting in skeletal rearrangement and isomer composition. Announces oligomeric synthetic lubricants. The claimed composition is not greater than a trimer to tetramer ratio of 1 to 1. The branching ratio has not been announced.

Coordination catalyst, especially silica support preparation of higher polymers from 1-alkanes using chromium catalyst on body'm connexion Jour.Catalysis 88 in Weiss et al., Described in 424-430 (1984) and German Offenlegungsschrift 3,427,319 Have been. The above methods and products therefrom will be described in detail below in comparison with the methods and products of the present invention.

It is processing which is well-known that Lewis acids such as promoted BF ₃ and (or) metal halide may contact the Friedel-Crafts reaction. However, the olefin oligomers, especially the PAO oligomers, have the starting 1-olefin 2
It is produced by a method in which heavy bond isomerization easily occurs. As a result, the olefin oligomer has many short side chains. This side chain reduces the lubricity of the lubricant.

Liquid hydrocarbon lubricant compositions of the present invention is C ₆ -C ₂₀ 1-alkenes has been oligomerization Karae the surprisingly have has moreover surprisingly low pour point as well a high viscosity index (VI). The composition consists of C ₃₀ -C ₁₃₀₀ hydrocarbon, branched ratio 0.1
9 or less; weight average molecular weight 300 to 45,000; number average molecular weight 300
~ 18,000; molecular weight distribution 1 ~ 5 and pour point -15
It is below ° C.

A new composition consisting of 11-octyldocosane having the following formula:

The composition was found to exhibit good lubricity either alone or in admixture with 9-methyl, 11-octylheneicosane. Surprisingly this mixture is more than 130, preferably 1
Has a viscosity index of 30 to 280 while maintaining a pour point below -15 ° C. These compositions are representative of the present invention.
Consists C ₃₀ H ₆₂ alkanes, 0.19 or less, preferably has a branching ratio or CH ₃ / CH ₂ ratio of 0.10 to 0.16. This low branching ratio and pour point characterize the inventive compositions herein referred to as polyalpha-olefins or HVI-PAO, and have a particularly high viscosity index compared to commercially available polyalpha-olefin (PAO) synthetic lubricants. Give to this composition.

The unique lubricant oligomers of the present invention are also produced in a wide range of molecular weights and viscosities, with branching ratios of less than 0.19 and about 1.05
Or consisting of C ₃₀ -C ₁₀₀₀ hydrocarbon with a molecular weight distribution of 2.5. The oligomer can be mixed with conventional mineral oils or greases of other properties to give compositions with significant lubricity.

The composition of the present invention is capable of converting an alpha-olefin, such as 1-decene, under oligomerization reaction conditions to VI B of the IUPAC periodic table.
It can be oligomerized and produced by contacting with a group III supported reduced valence state metal oxide catalyst. Chromium oxide is a preferred metal oxide.

The present invention provides a process for preparing liquid oligomers of olefins, such as 1-decene, having a higher viscosity index than oligomers having a branching ratio of 0.19 or less and higher branching ratios. These low branch ratio oligomers have improved viscosity-
It can be used as a base material for many lubricants or greases having temperature relationships, oxidation stability, volatility, and the like. They can also be used to improve the viscosity and viscosity index of low quality oils.
For example, olefins can be oligomerized over supported and reduced metal oxide catalysts from Group VIB of the Periodic Table to make oligomers suitable for lubricant applications. In particular, the present application relates to a process for the oligomerization of olefinic hydrocarbons in which hydrocarbons having from 6 to 20 carbon atoms are oligomerized under oligomerization conditions, wherein the reaction product is substantially less than the non-isomerized olefin. For example, where most of the double bonds of olefins or olefinic hydrocarbons are not isomerized in the presence of a suitable catalyst, such as a supported and reduced metal oxide catalyst from Group VIB of the Periodic Table.
-Alpha-olefins such as decene.

The use of reduced group VIB chromium-containing metal oxides on inert supports is a novel technique for oligomerizing liquid olefins suitable for high quality lubricating oils.

 FIG. 1 is a comparison diagram of PAO and HVI-PAO synthesis.

 FIG. 2 is a VI comparison diagram of PAO and HVI-PAO.

 FIG. 3 shows the pour points of PAO and HVI-PAO.

FIG. 4 shows the C-13 NMR spectrum of HVI-PAO from 1-hexene.

FIG. 5 shows the C-13 NMR spectrum of 5csHVI-PAO from 1-decene.

FIG. 6 shows the C-13 NMR spectrum of 50csHVI-PAO from 1-decene.

FIG. 7 shows the C-13 NMR spectrum of 145csHVI-PAO from 1-decene.

FIG. 8 shows a gas chromatograph of HVI-PAO 1-decene trimer.

FIG. 9 shows a C-13 NMR spectrum of HVI-PAO 1-decene trimer.

FIG. 10 shows C-13 NMR calculations versus measured chemical shifts of the HVI-PAO 1-decene trimer component.

Unless otherwise indicated, all HVI-PAO oligomers or lubricants in the following description refer to hydrogenated oligomers and lubricants in accordance with methods well known to those skilled in the art of making lubricants. Upon oligomerization, the HVI-PAO oligomer is a mixture of a dialkyl vinylidene system and a 1,2-dialkyl or trialkyl mono-olefin. The low molecular weight unsaturated oligomer may be hydrogenated to provide a heat and oxidation stable lubricant. High molecular weight unsaturated HVI-PAO oligomers are sufficiently thermostable and can be used without hydrogenation. Both low or high molecular weight unsaturated hydrogenated HVI-PAOs have a viscosity index of at least 130, preferably 130 to 180 and -15 ° C.
Hereinafter, a pour point of preferably -45 ° C is shown.

In FIG. 1, the novel oligomer or high viscosity index polyalpha-olefin (HVI-PAO) of the present invention is shown in a comparison diagram with ordinary polyalpha-olefin (PAO) from 1-decene. The new reduced chromium catalyzed polymerization reaction described below yields oligomers that are substantially free of double bond isomerization. Ordinary PAOs promoted by one-sided BF ₃ or AlCl ₃ generate carbonium ions, which in turn promote isomerization of olefinic bonds and polyisomer formation. HVI-PAO produced in the present invention CH of PAO ₃ / CH ₂ ratio of 0.02
Compared to the above, it has a structure with a ratio of 0.19 or less.

FIG. 2 shows the viscosity index versus viscosity relationship for HVI-PAO and PAO lubricants, with HVI-PAO at all tested viscosities.
Obviously, O is superior to PAO. HV-P as indicated by the branching ratio resulting in improved viscosity index (VI)
Despite the more regular structure of AO oligomers, these
It is worth noting that it shows a better pour point than PAO. It is expected that oligomers having a normal structure having a few isomers will have a high solidification temperature and a high pour point, and their utility as a lubricant will be low. Surprisingly, however, this is not the case with the HVI-PAO of the present invention. FIGS. 2 and 3 show the superiority of HVI-PAO in both fluidity and VI.

The novel HVI-PAO oligomer production method described herein is 300 to
It has been discovered that it can be tailored to produce oligomers having a weight average molecular weight of 45,000 and a number average molecular weight of 300 to 18,000. Molecular weight by measurement carbon atoms over a C ₃ to C _1300, the viscosity is in the 100 ° C. until ^{750mm 2 / s (cs),} 500mm in viscosity 100 ° C. in the range of C ₃₀ to C ₁₀₀₀ ² /
Up to s (cs), preferably 3 to 750 mm ² / s.
The molecular weight distribution (MWD), defined as the weight average molecular weight to number average molecular weight ratio, is between 1.00 and 5, preferably between 1.01 and 3, and most preferably between about 1.05 and 2.5. Compared to 1-alkenes of BF ₃ or AlCl ₃ catalytic polymerization Karae was normal PAO, HVI-PAO of the present invention it was divide molecular ratio of high molecular weight polymer in the product is high.

The viscosity of the new HVI-PAO at 100 ℃ is 3 to 5000mm ² / s
(Cs). The viscosity index of the new PAO is approximately given by: VI = 129.8 + 4.53 × (V ₁₀₀ ° C.) ^0.5 where V ₁₀₀ ° C. is the kinematic viscosity measured at 100 ° C. in centistokes.

It has been found that the novel oligomer compositions of the present invention exhibit a unique structure beyond the important properties of branching ratio and molecular weight. The dimer and trimer were separated by distillation and their components were further separated by gas chromatography. Lower oligomers and components along with the complete reaction mixture of HVI-PAO oligomers were analyzed by infrared spectroscopy and C-13NM
Studied by R. This makes it possible, in particular, to use ordinary PAOs produced by BF ₃ , AlCl ₃ or Ziegler-type contacting.
It was confirmed that the product of the present invention had a highly uniform structural composition as compared with Comparative Example. The ability of C-13 NMR to identify structural isomers leads to the identification of specific compounds in lower oligomer moieties. More homogeneous isomer mixtures in higher molecular weight oligomers can be compared with the discovery of low branching ratios and good viscosity indices. Useful for confirmation.

1-hexene HVI-PAO oligomers of the present invention is very uniform linear C ₄ branched chain has also normal head - shows that with tail connection. In addition to the structure from the normal head-to-tail connection, the backbone structure shows the following structure as confirmed by NMR:
Has some head connections: The NMR poly (1-hexene) spectrum is shown in FIG.

Oligomerization of 1-decene with supported chromium in the reduced valence state also results in HVI-PAO having a structure similar to that of the 1-decene oligomer. After distillation to remove light parts and hydrogenation, the lubricant product has C-13 NMR spectral characteristics. Figures 5, 6 and 7 show the viscosity at 100 ° C of 5 mm ² / s (c
s), typically with a 50mm ² / s (cs) and 145mm ² / s (cs)
3 shows a C-13 NMR spectrum of HVI-PAO.

Table A below shows the NMR data of FIG. 5, Table B shows the NMR data of FIG. 6, and Table C shows the NMR data of FIG.

In general, new oligomers Has a normal head-to-tail structure where n is 3 to 17 and some head-to-head connections.

Trimer of 1-decene HVI-PAO oligomer is obtained from the oligomerization mixture at 165-210 ° C. and 13.3-26.6 Pa (0.1-0.2 torr).
At 20 mm ² / s (cs) in a short circuit device by distillation from synthetic HVI-PAO. The non-hydrogenated trimer shows the following viscosity measurements: V ＠ 40 ° C. = 14.88 mm ² / s (cs); V ＠ 100 ° C. = 3.67 mm ² / s (cs): VI = 137.

The trimer is hydrogenated at 235 ° C using Ni and 4200 KPaH ₂ on Kieselguhr hydrogenation catalyst to give hydrogenated HVI with the following properties:
-PAO trimer is obtained: V ＠ 40 ° C. = 16.66 mm ² / s (cs); V ＠ 100 ° C. = 3.91 mm ² / s (cs): VI = 133. Pour point -45 ° C or less.

Gas chromatographic analysis of the trimer shows that it consists essentially of two components with retention times of 1810 and 1878 seconds under the following conditions: Gas chromatograph (gc) column-60 m ID 0.32 mm capillary column Is coated with 0.25 mm thick stationary phase SPB-1 and is commercially available from Shuperco Chromatograph Surprise as Catalog No. 2-4046.

Separation conditions-Model 3700 Varian gas chromatograph with a flame ionization detector and a capillary inlet with a split ratio of about 50. The N ₂ carrier gas flow rate is 2.5 ml / min. Inlet inlet temperature 300 ° C, detector inlet temperature 330 ° C; Column temperature is initially 45 ° C for 6 minutes and final 300 ° C at a rate of 15 ° C per minute.
Heat at 300 ° C for 60 minutes. Sample injection size 1μl
It is. Under these conditions, the retention time of gc standard n-dodecane is 968 seconds.

 A representative chromatograph is shown in FIG.

The C-13 NMR spectrum of the distilled _C30 product (FIG. 9) confirms the chemical structure. Table D shows the C-13 NMR data of FIG.

The individual peak assignments of the C-13 spectrum are shown in FIG. The calculated chemical shift based on this structure is shown in FIG. 10 and is in good agreement with the measured chemical shift. Calculations of hydrocarbon chemical shifts were performed as described in "C-13 NMR for Organic Chemists", Chapter 3, pages 38-41 (1972) by GC Revey and GL Nelson of Jyon Wille & Sons. The components were identified as 9-methyl, 11-octylhneicosane and 11-octyldocosan by infrared and C-13 NMR analyses, and the ratio of heneicosane to docosane was 1:10.
It was found that the ratio was about 10: 1. The hydrogenated 1-decene trimer produced by the method of the present invention is at 60 ° C.
Has a refractive index of 1.4396.

The process of the present invention is carried out industrially by BF ₃ or AlCl ₃
Use 1- Produces a surprisingly simple and convenient dimer compared to the dimer produced by alkene oligomerization. In the present invention, most of the non-hydrogenated dimerized 1-alkene is represented by the formula CH ₂ CR ₁ R ₂ (where R ₁ and R ₂ are alkyl groups each representing a residue from the head-to-tail addition of the 1-alkene molecule). Has a vinylidene structure such as For example, it has been found that the 1-decene dimer of the present invention has only three major components when examined by gc. Based on C-13 NMR analysis, the non-hydrogenated components were 8-eicosene, 9-eicosene, 2-octyldodecene and 9-methyl-8 or 9-methyl-9.
-It was discovered that it was nonadecene. The hydrogenated dimer components were determined to be n-eicosene and 9-methylnonacosan.

The olefin used as starting material in the process of the invention is C ₆
-C ₂₀ linear 1-olefins such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, etc., Oil spills may also be used. More preferred are 1-heptene to 1-hexadecene, and particularly preferred are 1-olefins from 1-octene to 1-tetradecene. These C ₆ -C ₂₀ linear 1-olefin requires that occupy all or main part of the olefins of the starting materials. The bonding system of the resulting oligomer is mainly based on a head-to-tail and / or head-to-head bond based on a 1-olefin as a starting material, not a so-called gem-dialkyl structure.

The oligomers of alpha-olefins according to the invention have a lower branching ratio of less than 0.19 and better lubricity than alpha-olefins with a high branching ratio as produced by known industrial processes.

This new type of alpha-olefin oligomer is produced by an oligomerization reaction in which most of the alpha-olefin double bond is not isomerized. These reactions include alpha-olefin oligomerization with supported metal oxide catalysts such as Cr-on-silica compounds or other supported Group VIB compounds of the Periodic Table. The best catalyst is a low valent 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. A porous substrate having an opening of at least 40 × 10 ⁻⁴ μm is preferred.

The support material usually has a high surface area and an average pore size of 40 to 350.
It has a large pore volume of × 10 ^-4 μm. The high surface area supports a large amount of the highly dispersible active chromium metal center and is convenient for obtaining the maximum effect of metal utilization, making it a highly active catalyst. The support is at least 40 × 10 ⁻⁴ μm, preferably 60 to 300 × 10 ⁻⁴ μm
m must have a large average aperture. This large aperture increases catalyst productivity because it does not restrict the diffusive traffic of lubricants and products to the active metal center. Also, for this catalyst which is used in a fixed bed or slurry reactor and which is recirculated multiple times, a silica substrate of high physical strength is preferred to prevent abrasion or crushing of the catalyst particles during handling or reaction.

The supported metal oxide catalyst may be produced by impregnating a metal salt in water or an organic solvent on a support. Appropriate known organic solvents such as ethanol, methanol or acetic acid can be used. The solid catalyst precursor is then dried at 200 to 9
Fired at 00 ° C in air or other oxygen containing gas. Catalyst then various reducing agents, for example _{CO, H 2, NH 3,} H 2 S, C
S ₂ , CH ₃ SCH ₃ , CH ₃ SSCH ₃ , a metal alkyl-containing compound such as R ₃ Al, R ₃ B, R ₂ Mg, RLi, R ₂ Zn (where R is alkyl,
Alkoxy, aryl, etc.). CO or H ₂ or metal alkyl containing compounds are preferred.

Group VIB metal compounds can also be applied to reduced substrates such as Cr II compounds. The obtained catalyst is below room temperature to about 250 ℃
Up to, preferably 90-250 ° C, most preferably 100-180 ° C
At 10.1KPa (0.1 atm) to 34500KPa (5000Psi)
Is very active in the oligomerization of olefins. The contact time between the olefin and the catalyst can vary from 1 second to 24 hours. The weight hourly space velocity (WHSV) is 0.1 to 10 based on the total catalyst weight. The catalyst can be used in a batch reactor or a fixed bed continuous flow reactor.

Generally, the support material is added to a metal compound such as an acetate or nitrate solution, and then the mixture is mixed and dried at room temperature. The dried solid gel is gradually raised and purged at 600 ° C. for 16-20 hours. The catalyst is then cooled to a temperature of 250-450 ° C. in an inert atmosphere and contacted with a stream of pure reducing gas to effect a sufficient catalytic reduction through sufficient CO so that the catalyst changes from light orange to pale blue and changes color. Generally, the catalyst is treated with a stoichiometric excess of twice the CO equivalent to reduce the catalyst to a lower valence state. At the end, the catalyst is cooled to room temperature and ready for use.

The product oligomer has a wide range of viscosities and a high viscosity index, making it suitable for high performance lubrication applications. The oligomers also have an aggressive molecular structure with very uniform head-to-tail connections and some head-to-head connections. These low branch ratio oligomers have a high viscosity index of at least 15-20 units, typically 30-40 units, and are typically higher than the equivalent viscosities of conventional oligomers having a high branch ratio and a corresponding low viscosity index. . These low-branched oligomers maintain better or comparable pour points. The branching ratio defined as the ratio of CH ₃ groups to CH ₂ groups in the lubricating oil is Analytical Chemistry Volume 25, No. 1
0, 1466 (1953), calculated from the weight part of methyl group obtained from the infrared method.

As noted above, the supported Cr metal oxides in different oxidation states can be converted to C ₃ -C using a catalyst produced by CrO ₃ on silica.
It is known to polymerize ₂₀ alpha olefins.
(HL Claus DE.3427319 and Journal of Catalys
is 88,424-430 (1984))
It is said that the following occurs at low temperatures to produce adhesive polymers and at high temperatures the catalyst promotes isomerization, cracking and hydrogen transfer reactions. The present invention produces low molecular weight oligomer products using catalysts that minimize side reactions such as 1-olefin isomerization, cracking, hydrogen transfer and aromatization under reaction conditions. Due to the production of this novel low molecular weight product suitable for use as a lubricating oil main raw material or as a mixture with other lubricating oil raw materials, the reaction of the present invention is carried out at a temperature higher than that suitable for producing high molecular weight polyalpha-olefins (90-2
50 ° C). The catalyst used in the present invention does not significantly undergo side reactions even at high temperatures when oligomeric low molecular weight fluids are produced.

The catalysts of the present invention produce low molecular weight polymers with high efficiency by minimizing all side reactions other than the oligomerization of alpha olefins. It is well known in the art that chromium oxides, especially pure or supported chromia, in the mean +3 oxidation state, come into contact with double bond isomerization, dehydrogenation, cracking, and the like. Although the actual properties of the supported Cr oxides are difficult to detect, the catalysts of the present invention support a large amount of Cr (II) on silica, which is highly isomerized, cracked or hydrogenated at high reaction temperatures. Strong contact with Alpha-Olefin oligomerization without causing or the like. However, the catalysts produced in the above references can be more rich in Cr (III). They contact the alpha-olefin polymerization reaction at low reaction temperatures to produce high molecular weight coalescence. However, at elevated temperatures, undesirable isomerization, cracking and hydrogenation reactions occur as described in the literature. Conversely, high temperatures are required in the present invention for lubricant production. In the past, it has also been said that supported Cr catalysts rich in Cr (III) or in a highly oxidized state are catalyzed by 1-butene isomerization which has 10 ³ higher activity than the polymerization of 1-butene. Catalyst quality, manufacturing methods, processing and reaction conditions are important to the contact performance and composition of the product, which distinguishes the prior art from the present invention.

In the present invention, low catalyst concentrations of 10 to 0.01% by weight, based on feed, are used for oligomer production. On the other hand, the literature uses a catalyst ratio of 1: 1 on feed basis for the production of higher polymers. Relying on a low catalyst concentration in the present invention for the production of low molecular weight materials is contrary to conventional polymerization theory as compared to literature results.

The oligomers of 1-olefin prepared according to the invention generally have a lower molecular weight than the semi-solid very high molecular weight polymers produced in the literature. These higher polymers are not suitable as main raw materials for lubricants and usually do not include the detection amount of dimer or trimer (C ₁₀ -C ₃₀ ) components from synthesis. This higher polymer also has very little unsaturation. However, the products according to the invention are liquids which are free-flowing at room temperature, are suitable for lubricating oil base stocks, contain considerable amounts of dimers or trimers and are highly unsaturated.

The following examples of the invention are merely illustrative and do not limit the scope of the invention.

Example 1 Catalyst Preparation and Activation methods chromium acetate _{(II) (Cr 2 (OCOCH} 3) 4 2H 2 O) 1.9g (5.58 mmol) (commercially available) was dissolved in hot acetic acid 50 ml. 8-12 silica gel with large mesh, surface area 300m ² / g, pore volume 1ml / g
50 g were added. The liquid was almost completely absorbed by the silica gel. The mixture was mixed on a room temperature rotavap for 30 minutes, placed in a dish and dried at room temperature. First, 20 g of dry solids were purged with N ₂ at 250 ° C. in a tube furnace. The furnace temperature was raised to 400 ° C. in 2 hours to 600 ° C., purged with dry air for 16 hours, and then cooled to 300 ° C. with N ₂ . Next, a pure CO (Mateson 99.99%) flow was allowed to flow for 1 hour, and then cooled to room temperature through N ₂ to be used.

The catalyst 3.2g prepared in Example 1 was placed in a dry box N ₂ atmosphere 3/8 tubular stainless steel reactor. The reactor was heated to 150 ° C. by a single zone Lindberg furnace. Pre-purified 1-hexene per hour at 965 KPa (140 psi)
It was sent to the reactor at a rate of 20 ml. The effluent was collected to remove unreacted starting materials and low boiling substances at 6.7 KPa (Hg, 0.05 mm). The residual clear colorless liquid had a viscosity and VI suitable for the lubricating oil main raw material.

Example 3 In the same manner as in Example 2, a newly formed catalyst sample was charged into a reactor, and
-Hexene was sent to the reactor at 101 KPa (1 atm) at a rate of 10 ml / h. As shown below, a lubricating oil with high viscosity and high VI was obtained. These tests show that high viscosity lubricating oil products can be obtained under different reaction conditions.

Example 4 An industrial chromium / silica catalyst containing 1% Cr on synthetic silica gel with large pore volume was used. The catalyst is first 800 ℃ in air
And then reduced with CO at 300 ° C for 1.5 hours. Then 3.5 g of the catalyst was packed in a tubular reactor and heated to 100 ° C. under N ₂ atmosphere. 28 ml / h of 1-hexene at 101 KPa (1 atm)
In the proportion of The product was collected for the following analysis: These tests show that the different Cr on the silica catalyst is also effective in oligomerizing olefins into lubricating oil products.

Example 5 Purified 1-decene was prepared in the same manner as in Example 4 from 1830 to 2310 KPa (2
(50-320 psi) through the reactor. Products were collected periodically to remove low boiling products below 343 ° C (650 ° F).
High quality lubricating oil with high VI was obtained.

(See Table F) Example 6 A similar catalyst was used for the 1-hexene oligomerization test at different temperatures. 28 ml of 1-hexene was supplied at 101 KPa (1 atm) per hour.

Example 7 1.5 g of the same catalyst as prepared in Example 4 was added under N ₂ atmosphere.
Into the neck flask was added 25 g of 1-hexene.
The slurry was heated at 55 ° C. for 2 hours under N ₂ atmosphere. Next, a small amount of heptane solvent was added to separate the catalyst. The solvent and unreacted starting materials were removed to give a mucus yield of 61%. This mucus is 100
1536 and 51821 mm ² / s at ° C and 40 ° C respectively
It had a viscosity of (cs). This example showed that the reaction could also be performed with a batch operation.

The following 1-decene oligomer was synthesized by the reaction of purified 1-decene with an activated chromium catalyst on silica. Activating catalyst is chromium acetate on silica gel (1 or 3% Cr)
After baking at 500-800 ° C for 16 hours, the catalyst is baked with CO at 300-350 ° C1
Manufactured with time treatment. 1-Decene was mixed with the activated catalyst and heated to the reaction temperature for 16-21 hours. Next, the catalyst was taken out and the viscous product was distilled at 200 ° C. and 13.3 KPa (Hg 0.1 mm) to remove low boiling components.

The reaction conditions and results of lubricating oil synthesis of HVI-PAO are as follows: Example 8-11 Branching Ratio and Lubricating Oil Properties of Alpha Olefin Oligomers Branching ratio and lubricating oil properties of conventionally manufactured alpha-olefin oligomers These samples are commercially available. These have higher branching ratios than the samples shown in Table 2. They also have lower VI values than the previous sample.

Comparing these two sets of lubricants, lower than 0.19 of an alpha olefin such as 1-decene, preferably 0.13
Oligomers with a branching ratio of 0.10.18 are clearly better lubricants with higher VI. The examples produced according to the invention have a branching ratio of 0.14 to 0.16 and
Range from 3 to 483.1 cs and 130 to 280
Excellent lubricating oil with a viscosity index of

Example 16 An industrial Cr on silica catalyst containing 1% Cr on large pore volume synthetic silica gel was used. The catalyst was first calcined in air at 700 ° C for 16 hours and reduced in CO at 350 ° C for 1-2 hours. In a suitable reactor, 1 part by weight of the activated catalyst was added to 200 parts by weight of 1-decene and heated to 185 ° C. 2-3.5 parts of 1-decene was continuously added to the reactor per minute, and 0.5 part by weight of catalyst was added per 100 parts of 1-decene feed. After adding 1200 parts of 1-decene and 6 parts of the catalyst, the slurry was stirred for 8 hours, and the catalyst was removed to remove light products boiling at 150 ° C. or less at 0.1 mm of Hg. The residual product was hydrogenated at 200 ° C. over Ni on Kieselguhr catalyst. The final product has a viscosity of 18.5 mm ² / s (cs) at 100 ° C, VI 165 and pour point-
It was 55 ° C.

Example 17 Example 17 was repeated except that the reaction temperature was 125 ° C. The final product has a viscosity of 145mm ² / s (cs) at 100 ° C, 2
It had a VI of 14 and a pour point of -40 ° C.

Example 18 Example 16 was repeated except that the reaction temperature was 100 ° C. The final product has a viscosity of 298cs at 100 ° C, VI of 246 and -3
It had a pour point of 2 ° C.

The lubricating oil products of Examples 16 to 18 had the following dimer and trimer and isomer distributions.

These three examples show that the new HVI-PAO with a wide viscosity contains dimers and trimers with unique structures in various proportions.

Molecular weights and molecular weight distributions were analyzed using a high pressure fluid chromatograph consisting of a Constametric II high pressure, Milton Roy binary piston pump and a Tracoll 945 LC detector. During analysis, the system pressure is 4600KPa (650ps
i), and the THF solvent (HPLC grade) discharge rate was 1 ml / min. The detector block temperature was set at 145 ° C. 1g PAO
1 ml of the sample dissolved in 1 ml of THF solvent was injected into the chromatograph. The sample was eluted through a series of the following columns from Water Associates: Ustrastyragel 10
⁵ A, P / N10574, Utorasuchirageru 10 ⁴ A, P / N10573, Utorasuchirageru 10 ³ A, P / N10572, Utorasuchirageru 500A,
P / N10571. The molecular weight is PAO available from Mobil Chemical,
Corrected for mobile SHF-61 and SHF-81 and SHF-401.

The following table summarizes the molecular weights and distributions of Examples 16-18.

Viscosity as low as 3 mm ² / s (cs) and 500 mm ² / s under the same conditions
HVI-PAO with high viscosity (cs) and VI of 130-280
Products can be manufactured.

Ethene can be used as a starting material for conversion to higher C ₆ -C ₂₀ alfa olefins by conventional catalytic methods, for example Ch
em System Process Evaluation / Research Planning Rep
According to the synthesis method described in ort-Alpha Olefins. Report No. 82-4, ethene is brought into contact with a Ni catalyst at 80 to 120 ° C. at 7000 KPa (1000 psi). Intermediate Alpha Olefin is C ₆
-C Has a wide distribution in the ₂₀ carbon range. The full range of alpha olefins or subranges such as C ₆ -C ₁₄ from the growth reaction can be used to produce high yield lubricating oils with a high viscosity index. The oligomer after hydrogenation has a low pour point.

Example 19 Equimolar C ₆ -C ₈ -C ₁₀ -C ₁₂ -C ₁₄ -C ₁₆ -C ₁₈ -C ₂₀ Above
Was reacted at 130 ° C. with a ₂ % by weight activated Cr / SiO ₂ catalyst in a nitrogen atmosphere. After 225 minutes of reaction, the catalyst was separated, and the reaction mixture was distilled to obtain H.
Light fractions of 120 ° C. or less with a g of 0.1 mm were removed. It had a V ₁₀₀ ° C of 67.07 cs and a VI of 195 with a residual lube yield of 95%.

Example 20 An equimolar amount of the above C ₆ -C ₂₀ alpha olefin mixture was continuously fed over an activated Cr / SiO ₂ catalyst in a tubular reactor. The results are as follows.

Example 21 An equimolar olefin mixture of C ₆ -C ₈ -C ₁₀ -C ₁₂ -C ₁₄ was reacted on the same Cr / SiO ₂ catalyst as in Example 2. The results are shown in Table 2 below
Shown in 1.

Since the alpha olefin range from the ethylene growth reaction and metathesis process can be used for the production of high-grade lubricating oils according to the process of the present invention, this process is cheaper and more flexible than using pure single monomers.

Example 22 Using a Group VIB metal species, tungsten or molybdenum, different from the standard 1-decene oligomerization synthesis described above.
Repeated at 5 ° C. W or MO treated porous substrate with CO at 460 ℃
To 1% by weight of the reduced oxidation state metal. The molybdenum catalyst provided a mucus yield of 1%. Tungsten produced only C ₂₀ dimer.

The use of supported Group VIB oxides as olefin oligomerization catalysts for the production of low branching ratio lubricating oil products with low pour points has not been previously known. No catalytic process has been known for producing lubricating oils without a corrosive cocatalyst of oligomers with a low branching ratio structure and with a wide range of viscosities and good VI, especially branching smaller than about 0.19 The production of lubricating oils with a ratio has never been known before.

Although the present invention has been described in terms of a preferred embodiment, those skilled in the art will appreciate that modifications and variations can be made without departing from the spirit and scope of the invention. Such modifications and variations are considered to be within the scope of the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁶ Identification symbol FI // C10N 20:04 C07B 61/00 300 20:00 30:02 70:00 C07B 61/00 300 (58) Field surveyed ( Int.Cl. ⁶ , DB name) C10M 5/04 C10N 20:00 C10N 70:00

Claims (14)

(57) [Claims] 1. A C ₃₀ -C ₁₃₀₀ hydrocarbon, comprising a branching ratio of less than 0.19, a weight average molecular weight of 300 to 45,000, a number average molecular weight of 300 to 18,000, a molecular weight distribution of 1 to 5 and -15 ° C. or lower. Liquid lubricant characterized by having a pour point of: 2. A composition having a viscosity index of 130 or more and 3 at 100 ° C.
Or lubricating agent according to claim 1 having a viscosity of 750 mm ² / s. 3. The lubricant of claim 1 having a _C30 cut having a branching ratio of less than 0.19, a viscosity index of 130 or more and a pour point of -45 ° C. or less. The lubricant of claim 1 consisting of oligomers with head-to-tail and / or head-to-head bond trimer or higher oligomers of wherein linear C ₆ -C ₂₀ 1-alkenes. 5. A lubricant according to claim 4, wherein said oligomer comprises a 1-decene oligomer. 6. A liquid lubricant comprising a mixture of _C30 alkanes consisting essentially of 9-methyl, 11-octylhneicosane and 11-octyldocosane. 7. A 9-methyl, 11-octylheneicosane pair
The lubricant according to claim 6, wherein the molar ratio of 11-octyldocosane is from 1:10 to 10: 1. 8. A liquid lubricant comprising a C ₃₀ H ₆₂ alkane having a branching ratio of less than 0.19 and a pour point of -15 ° C. or less. 9. The method according to claim 9, wherein the alkane is 3 to 4 cs at 100 ° C.
The lubricant of claim 8 having a viscosity of 130 or more, a viscosity index of 130 or more and a pour point of -45 ° C or less. 10. The structural formula: A liquid lubricant comprising 11-octyldocosan having the formula: 11. An olefin having 6 to 20 carbon atoms or a mixture of said olefins is pre-oxidized with a chromium catalyst on a porous support at a temperature of 200 to 900 ° C. in the presence of an oxidizing gas, and then said catalyst is treated. A chromium catalyst treated with a reducing agent for a time and at a temperature sufficient to reduce to a lower valence state than Cr (III) is brought into contact with a chromium catalyst at a reaction temperature of 90 to 250 ° C. to obtain a C ₃₀ -C ₁₃₀₀ hydrocarbon. Consisting of a branching ratio of less than 0.19, a weight average molecular weight of 420 to 45,000, 420
A process for producing a liquid hydrocarbon suitable as a main raw material for a lubricant, comprising producing an oligomeric liquid product having a number average molecular weight of from 18,000 to 18,000 and a pour point of -15 ° C or lower. 12. The reducing agent comprises CO, the oligomerization temperature is 100-180 ° C. and the yield of C ₃₀ ⁺ oligomer is 100
12. The method according to claim 11, which is at least 85% by weight of the product having a viscosity of at least 15 cs at ° C. 13. The method according to claim 12, wherein the support is porous silica. 14. The olefin is essentially 1-octene, 1
13. The method according to claim 12, comprising -decene, 1-dodecene, 1-tetradecene or a mixture thereof.