JP3032806B2 - Oligomerization of C 2 -C 5 olefins with reduced chromium catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a C ₂ -C ₅ alpha-
The present invention relates to a method for oligomerizing an olefin raw material and an olefin oligomer produced by the method. In particular, the present invention, C ₃ -C ₅ alpha using reduced chromium oxide on a solid support as catalyst - a mixture of olefins or C
₃ -C ₅ alpha - a mixture of olefin and ethylene relates to a method for oligomerization. Oligomer products, either C ₃ -C ₅ olefin co- oligomer or C ₃ -C ₅ olefin and ethylene co-oligomer, are excellent quality lubricants and lubricant additives that exhibit high viscosity indices. For example, it is useful as a viscosity index improver and as a chemical intermediate.

[0002]

BACKGROUND OF THE INVENTION Efforts to improve the performance of lubricants based on natural mineral oils by the synthesis of oligomeric hydrocarbon fluids have been an important research and development subject in the petroleum industry for at least 50 years, primarily with alpha-olefins or 1-olefins. -Led to the relatively recent market introduction of a number of excellent polyalpha-olefins (PAOs) based on alkene oligomerization. With respect to improving the properties of lubricants, the focus of industry research efforts on synthetic lubricants is to show a useful viscosity over a wide range of temperatures, ie, an improved viscosity index (VI), while also being equal to or less than mineral oil. Suitable for fluids that exhibit better lubricity, thermal and oxidative stability and pour point. These new synthetic lubricants reduce friction and therefore increase mechanical efficiency over a wide range of mechanical loads, from worm gearing to traction drives, and over a wider range of operating conditions than mineral oil lubricants. It is.

[0003] Catalysts found to be useful in the prior art for oligomerization of alpha-olefins to PAO include Lewis acids and Ziegler catalysts. The products are found to significantly change the properties of the lubricant depending on the catalyst used, and the economics of the process are also affected by the ease of separation, corrosiveness and other catalyst-dependent process characteristics. Bre
nnan "Ind. Eng. Chem. Prod. Re.
s. Dev. 1980, 19, 2-6 refer to the 1-decene trimer as an example of a structure that is compatible with a structure with excellent low temperature fluidity, where the concentration of atoms is determined by the center of the chain of carbon atoms. Very close to. It also describes the obvious dependence of the nature of the oligomer on the oligomer process, ie a cationic polymerization or Ziegler-type catalyst which is well known and practiced in the art.

The use of coordination catalysts, especially chromium catalysts on silica supports, to produce high polymers from 1-alkanes is described by Weiss et al. In "Jour.
s-is "88, 424-430 (1984) and DE-A-3427319. The methods and products therefrom are described in detail below in comparison to the methods and products of the present invention.

[0005] Despite their generally superior properties, PAO lubricants are often formulated with additives to enhance these properties for specific applications. Commonly used additives include, for example, Kirk-Othmer "En
cyclopedia of Chemical Tec
hnology, 3rd edition, Vol. 14, pages pp. 479-526, as described in Antioxidants, Rust Inhibitors, Metal Passivators, Antiwear Agents, Extreme Pressure Additives, Pour Point Depressants,
It includes detergent dispersants, viscosity index (VIB) improvers and antifoamers, and the literature is cited for a description of these additives and their use. Significant improvements in lubricant technology result from improvements in additives.

Recently, high VI lubricant compositions comprising polyalpha-olefins (here HVI-PAO and HVI-PAO)
The VI-PAO process) and their preparation using reduced chromium on a silica support as a catalyst are disclosed in U.S. Pat. Nos. 4,870,064 and 4,870,073. The method comprises contacting the chromium oxide catalyst reduced valence state on a porous silica support in oligomerization conditions in the oligomerization zone and C ₆ -C 20 _1-alkanes,
This produces a high viscosity, high VI liquid hydrocarbon lubricant having a branching ratio of less than 0.19 and a pour point of less than -15 ° C. The process is distinguishable in that little isomerization of the olefinic bond occurs compared to known oligomerization processes that produce polyalpha-olefins using Lewis acid catalysts. The lubricant produced in this way covers a sufficient range of lubricant viscosities and has a very high viscosity index (VI)
And a low pour point even at high viscosities.
The synthesized HVI-PAO oligomer has many terminal olefinic unsaturations.

Given the abundance of C ₂ -C ₅ alpha-olefins and their low cost in petroleum refining, if they are easy to handle, renewable and non-corrosive catalysts, high yield, high viscosity index lubrication It has long been recognized that they are a preferred source of low cost lubricants if they are oligomerized to yield agents. The olefin oligomers produced according to the present invention are characterized by a unique structure that gives the product particularly useful properties. In conventional Ziegler oligomerization of alpha olefins, the oligomers formed contain a high degree of structural or regioregularity as indicated by the multiple head-to-tail bonds in the oligomerization of these alpha olefins. In products from Ziegler-catalyzed oligomerization, up to 20% of the repeating units are linked by regular head-to-head and tail-to-tail linkages. However, in olefin oligomers formed from reduced metal oxide catalysts, at least 20% of the repeating units are linked by irregular head-to-head and tail-to-tail bonds. Therefore, these _C 3 -C ₅ alpha oligomer has at least 20% normal 20-40% of regio-irregularity, and in many cases, is 60% or less (100% regio regularity, Corresponding to a head-to-head linkage for the repeating oligomer unit). Thus, in many cases, 60-80% of the repeat bonds in the oligomer are linked by regular head-to-head bonds.

[0008]

SUMMARY OF THE INVENTION According to the present invention, C ₃ -C ₅ mixture or C ₃ -C ₅ olefin oligomer produced from an olefin and ethylene olefin is at least 20 normal 20
Has ４０40% regio-irregularity.

The oligomer can be formed by contacting a mixture of C ₃ -C ₅ alpha olefins with a reduced metal oxide catalyst, preferably reduced chromium oxide on a solid porous support. The catalyst is in the presence of an oxidizing gas 2
Oxidation at temperatures between 00 and 900 ° C. is then usually produced by treatment with a reducing agent at a temperature and for a time sufficient to reduce the oxide of the metal to a lower valence state.
Olefin oligomers are liquids having a viscosity of 10000 mm ² / s (cS) measured at 100 ° C. that are characteristically useful as lubricant bases or used as VI improvers. The oligomer can be hydrogenated to produce a saturated hydrocarbon product.

[0010] The process of the present invention comprises a mixture of C ₃ -C ₅ alpha-olefins or ethylene and C ₃ -C ₅ alpha-olefin.
Contacting the mixture of olefins with a chromium catalyst on a solid support, the catalyst comprising 200 to
Oxidation at a temperature of 900 ° C., followed by treatment with a reducing agent at a temperature and for a time sufficient to reduce the catalyst. Contact is useful as a lubricant substrate or V
1000 measured at 100 ° C. used as I improver
Occurs under conditions sufficient to produce a liquid olefin oligomer having a viscosity of 0 mm ² / s (cS). Oligomers can be hydrogenated to produce saturated hydrocarbons.

The produced olefin oligomer is separated by distillation to collect a gasoline boiling range overhead fraction, a distillate boiling range overhead fraction and a lubricating oil boiling range bottom fraction.

The present invention, C ₃ -C ₅ alpha - mixture or ethylene and C ₃ -C ₅ alpha-olefins - and cod in excellent yields the saturated hydrocarbon lubricant fraction from the oligomerization of a mixture of olefins, excellent The resulting products are particularly distinguished by a high viscosity index, which indicates the properties of the lubricant. Light oligomers or hydrocarbon fractions separated from the oligomerization mixture are useful as gasoline or distillate products.

Oligomeric products containing unsaturated double bonds are suitable as chemical intermediates for the subsequent functionalization, for example intermediates for the production of lubricant additives by reaction with maleic anhydride. Form an adduct that can be used as

In the following description, unless otherwise stated, references to the properties of the oligomer or lubricant of the present invention are:
For oligomers or lubricants that are simultaneously hydrogenated, hydrogenation of the oligomer product is usually preferred because it reduces residual unsaturation.

C ₃ -C ₅ alpha-olefin oligomers and oligomers of C ₃ -C ₅ -alpha-olefins with ethylene have a structure that is lower than that of conventional polyalphaolefins (PAO) from, for example, 1-decene. Unique. Polymerization with reduced metals such as chromium catalysts described below leads to oligomers that are substantially devoid of double bond isomerization. On the other hand, conventional PAOs promoted by BF ₃ or AlCl ₃ form carbonium ions, which in turn promote isomerization of olefinic bonds and the formation of multiple isomers. HVI-PAO generated in referenced invention
Has a CH ₃ /<0.19 compared to> 0.20 for PAO
It has a structure with a CHH ₂ ratio.

The C ₂ -C ₅ feedstock used in the present invention is a particularly inexpensive ordinary material found in petroleum refining complexes. Sources that are readily available include fluid catalytic cracker operation, especially the products of FCC unsaturated gas plants. Olefins can also be obtained from various steam cracking processes, such as light naphtha or liquefied petroleum gas (LP
G).

The mixture of propylene, 1-butene or 1-pentene and ethylene is 100: 1 to 1: 1 (C _3-
C _5: used in a molar ratio of _{C 2),} the molar ratio of about 20 to 1 is preferred.

Propylene, 1-butene or 1-pentene
For the oligomerization of ethylene and ethylene , the alpha-olefin can be used in pure form diluted with other inert materials. The liquid product after hydrogenation to remove unsaturation has a higher viscosity index than similar acid-catalysts such as aluminum chloride or similar alpha-olefins oligomerized with boron trifluoride. To produce a low molecular weight liquid product suitable for use as a lubricating oil feedstock or blended feedstock with other lubricating oil feedstocks, the oligomerization is carried out at a temperature higher than that suitable for producing high molecular weight polyalphaolefins ( 90-250 ° C.), but when using ethylene as a comonomer, lower temperatures, for example about 0 ° C., can be used, and the temperature range for the formation of ethylene-containing oligomers is typically from 0 to About 250
° C.

The present alpha-olefin oligomers are formed by an oligomerization reaction in which the predominant proportion of the double bonds of the alpha olefin is not isomerized. These reactions are carried out on supported metal oxide catalysts such as Cr on silica.
Compound or other supported IUPAC Periodic Table VIB
Includes oligomerization of alpha-olefins with group III compounds. The most preferred catalyst is a low valent Group VIB metal oxide on an inert support. Preferred supports include silica, alumina, titania, silica alumina, magnesia, and the like. The support binds the metal oxide catalyst. These porous substrates having openings of at least 40 × 10 ⁻⁷ mm are preferred.

The support usually has a large surface area and a large pore volume, with an average pore size of 40 to 350 × 10
^-7 mm (40-350 angstroms). The large surface area is advantageous for supporting large amounts of highly dispersible active chromium metal centers, and also allows for the most efficient use of the metal to obtain a very active catalyst. The support must have a large average aperture of at least 40 × 10 ⁻⁷ mm (40 Å) and> 6
An average aperture of 0-300 × 10 ⁻⁷ mm (> 60-300 Å) is preferred. This large opening
It does not impose any diffusivity restrictions on the reactants and products on the active catalytic metal center, thus further optimizing the productivity of the catalyst. Also, in order to use the catalyst in a fixed bed or slurry reactor and recycle and regenerate it multiple times, a porous support with good physical strength will reduce wear or disintegration of the catalyst particles during handling or reaction. Preferred to prevent.

[0016] The supported metal oxide catalyst is prepared by impregnating the support with a metal salt, preferably in water or an organic solvent. Any suitable organic solvent known to those skilled in the art can be used, for example, ethanol, methanol or acetic acid. The solid catalyst precursor is then dried and sintered at 200-900C with air or other oxygen containing gas. Then the catalyst, any couple of various well known reducing agents such as _{CO, H 2, NH 3,} H 2 S, CS 2, CH
₃ SCH ₃ , CH ₃ SSCH ₃ , metal alkyl containing compounds such as R ₃ Al, R ₃ B, R ₂ Mg, RLi, R ₂ Z
n where R is alkyl, alkoxy, aryl, and the like. Preferred is CO or H
₂ or a metal alkyl-containing compound.

On the other hand, Group VIB metals can be applied to substrates in a reduced form, for example a CrII compound. The obtained catalyst is 10 to 34600 kPa (0.1 atm to 5000 atm).
Very active in oligomerizing olefins at temperatures below room temperature, for example at a temperature of 0 ° C. to about 250 ° C. at a pressure of psi). The contact time of both the olefin and the catalyst is 1
Can vary from seconds to 24 hours. The catalyst can be used in a batch reactor, a continuous stirred tank reactor or a fixed bed continuous flow reactor.

Generally, the support material is added to a solution of a metal compound such as acetate or nitrate, and the mixture is then mixed and dried at room temperature. The dried solid gel is purged at an increasing temperature to about 600 ° C. for about 16-20 hours. Next, the catalyst is cooled to a temperature of about 250-450 ° C under an inert atmosphere, and a stream of pure reducing agent, eg, CO, is contacted with it. When enough CO passes to reduce the catalyst, there is a distinct color change from bright orange to light blue. Typically, the catalyst has an amount of C that is stoichiometrically equal to a two-fold excess to reduce the catalyst to a low valent CrII state.
O is processed. Finally, the catalyst is cooled to room temperature and used.

As indicated above, CrO ₃ on silica
Using more catalysts prepared C ₃ -C ₂₀ alpha - supported C in various oxidation states for polymerizing olefins
The use of r metal oxides is well known (H.L.K.
Raus, German Patent No. 3,427,319 and "Jou
rnal of Catalysis "88, 424-
430, 1984). The quoted statement states that polymerization occurs at low temperatures, usually below 100 ° C., to produce an adhesive polymer;
At higher temperatures, the catalyst teaches that it promotes isomerization, cracking and hydrogen transfer reactions. The method is
Liquid reaction low molecular weight oligomeric products are produced using reaction conditions and catalysts that minimize side reactions such as 1-olefin isomerization, cracking and hydrogen transfer and aromatization. Reduced metal oxide catalysts do not produce significant amounts of side reactions even at high temperatures producing oligomeric low molecular weight fluids. Therefore, these catalysts, while minimizing side reactions, oligomerize the olefins to yield high efficiency, low molecular weight polymers. Although the exact nature of the supported Cr oxide is difficult to determine, the catalyst of the present invention
Rich in Cr (II) supported on silica, it is more active to catalyze the oligomerization of alpha-olefins at elevated reaction temperatures without causing significant amounts of isomerization, cracking or hydrogenation reactions. is there. However, the catalysts described in the cited documents are rich in Cr (II),
They catalyze the polymerization of alpha-olefins at low reaction temperatures to produce high molecular weight polymers and, at higher temperatures, cause undesirable isomerization, cracking or hydrogenation reactions.

The catalyst of the present invention thus minimizes all side reactions, but oligomerizes olefins to yield high efficiency, low molecular weight polymers. It is well known to those skilled in the art that pure or supported chromium oxide, especially chromia having an average oxidation state of +3, catalyzes the isomerization, cracking and dehydrogenation of double bonds. However, catalysts such as those produced in the cited literature are rich in Cr (III). They catalyze the polymerization of alpha-olefins at low reaction temperatures to produce high molecular weight polymers. However, as the literature teaches, undesirable isomerization, cracking and hydrogenation reactions occur at elevated temperatures. In contrast, higher temperatures are required in the present invention to produce a lubricant product. The prior art also Cr (III) or high oxide-rich state supported Cr catalysts, teach the catalyst the 10 ³ high isomerization activity in 1-butene than polymerization of 1-butene I have. The quality of the catalyst, the preparation, the processing and the reaction conditions are important for the performance of the catalyst and for the composition of the product formed and distinguish the present invention from the prior art.

In the present invention, very low catalyst concentrations, based on 10% to 0.01% by weight of the feedstock, are used to produce oligomers, while in the cited literature,
A catalyst ratio based on a 1: 1 feed is used to produce the high polymer. Relying on low catalyst concentrations in the present invention to produce low molecular weight materials is contrary to conventional polymerization theory, as compared to the results of the cited literature.

The 1-olefin oligomer of the present invention is
It has a much lower molecular weight than the polymers produced in the cited literature, which are very high molecular weight semi-solids and are not suitable as lubricant raw materials. These high polymers, no dimers or trimers _{(C 10} ~C ₃₀₎ components in the amounts that can be detected from the normal morphing. These high polymers also have very low unsaturation. However, the products of the present invention are free flowing liquids at room temperature suitable for use as lubricating oil feedstocks and additives such as VI improvers.

Ethylene and C ₃ -C ₅ alpha-olefin or mixed C ₂ -C ₅ alpha-olefin are
A wide range of hydrocarbon products can be upgraded, either in diluted or pure form. High boiling components can be used as high quality lubricants with high viscosity index. The low boiling components can be used as feedstocks for gasoline, distillates or synthetic detergents, fuels, lubricants or additives to plastics. The catalyst for the conversion is a supported metal oxide, such as a Group VIB and VIIIB oxide catalyst on silica. The mixture of propylene, 1-butene or 1-pentene and ethylene is used in a molar ratio of 100: 1 to 1: 1, preferably a molar ratio of 20: 1.

[0024] C ₂ -C ₅ alpha - The use of a supported metal oxide catalyst was activated to produce a wide range of hydrocarbons from the olefin mixture is unique. The hydrocarbon lubricating oil fraction has a high viscosity index. The catalyst used in the present invention is a solid catalyst and is much easier to handle than conventional Ziegler catalysts and other solution catalysts. By-products with low boiling points are C ₅ -C ₃₀
Has the carbon number of These by-products have unsaturated olefinic double bonds and can be used as raw materials for the synthesis of detergent, fuel or lubricating oil additives. The catalyst used is non-corrosive and renewable.

[0025] In cage Goma of alpha - olefins may be used in pure form or diluted form to improve the quality gasoline distillates and lubricating oil products on a solid coordination catalyst. The products in the fuel range are high quality fuels with low sulfur and aromatic content. The lubricating oil product, after hydrogenation to remove unsaturation, has a higher viscosity index than alpha-olefins oligomerized with conventional acid catalysts such as aluminum chloride or boron trifluoride.

[0026] In the present invention, the lubricating oil composition from Oh oligomer of, measured at 100 ℃ 3mm ² / s~500
Produced with a viscosity of between 0 mm ² / s.

The product of the present invention exhibits a very unique structure that gives the product the properties of a novel composition. In conventional Ziegler oligomerization of alpha-olefins, the resulting oligomers have a high degree of structural or regioregularity, as indicated by the large number of head-to-tail bonds in the oligomerization of these alpha-olefins. Is well known to those skilled in the art. In products from Ziegler-catalyzed oligomerization, up to 20% of the repeating units are linked by head-to-head and tail-to-tail bonds. In the present invention, at least 40% of the repeating units are linked by head-to-head and tail-to-tail linkages. C _{3 of the} present invention
-C ₅ alpha - olefin oligomer comprises less than 60% regioregular, 100% regio regularity,
This corresponds to a head-to-tail bond for the repeating oligomeric unit.

In Table 1, the results of the spectroscopic measurements of the regioregularity of the invention are shown, together with the results from the products of the oligomerization of 1-decene and 1-hexene (No.
3-5). 1-decene, 1-hexene, 1-butene and (non-reactive nuclei enhanced by polarization moves) C-13 NMR spectra and INEPT of four prepared from HIV-PAO oligomerization process according Cr / SiO ₂ catalyst propene spectrum Is provided. For each oligomer,
The chemical shifts of the backbone methylene and methine carbons are calculated and assigned based on different combinations of regio-irregularities. 2 / Selective detection of methine carbon only
From the 4JINEPT spectrum, the amount of regioregularity of each oligomer is calculated. Entries 1 to 4 compare four different alpha-olefins as raw materials. Result is,
It shows that oligomers from higher olefins are formed in a more regioregular manner than lower olefins.

[0029]

[Table 1]

[0030]

The following examples illustrate the method of the present invention. In the invention, propylene and a mixture of ethylene and propylene are oligomerized using reduced chromium oxide on a silica support as a catalyst. The catalyst is prepared according to the method described in the previous example.
Examples 2,3,5,7,8,10.

Embodiment 1

Method for producing and activating a catalyst

1.9 g of chromium (II) acetate (Cr (O
COCH ₃ ) ₄ 2H ₂ O) (5.58 mmol) (commercially available) is dissolved in 50 ml of hot acetic acid. next,
50 g of silica gel (8 to 12 mesh size, 30
0 m ² / g surface area, 1 ml / g pore volume) is also added. Most of the solution is absorbed by the silica gel. The final mixture is mixed on a rotavap at room temperature for half an hour and dried at room temperature in an open dish. First, dry solids (20 g) are purged with N ₂ at 250 ° C. in a tube furnace. The furnace temperature is then raised to 400 ° C. for 2 hours. The temperature is then raised to 600 ° C
Purge dry air for 16 hours. The catalyst is then cooled to a temperature of 300 ° C. under N ₂ . Next, pure CO (9
(9.99% from Matheson) is introduced for 1 hour. Finally, the catalyst was cooled to room temperature under N _2, used.

Embodiment 2

[0035]

3 g of activated Cr / SiO ₂ catalyst was charged to a 9.5 mm (3.8 inch) inner diameter fixed bed down flow reactor. 5 g / h of propylene were reacted with the catalyst bed heated to 180-190 ° C. at 1620 kPa (220 psig). After 16 hours, 56.2 g of liquid product and 2
4.9 g of gas were collected. The gaseous product analyzed by gc contained 95% propylene. The liquid product is
It had the following composition: C ₆ (10.6), C ₉ (11.
2), C ₁₂ (8.6), C ₁₅ (7.4), C
₁₈ (3.3), C ₂₁ (3.9), C ₂₄ (2.
9), C ₂₇ (3.9), C ₃₀ (48.3) (% by weight).

The product of C _{6 to} C ₁₂ can be used as a gasoline component after hydrogenation. Product of C ₁₂ -C ₂₄ can be used as distillate components. Unhydrogenated lubricant products are most C ₂₇ and higher hydrocarbons, 180 ° C.
/13.3 kPa (0.1 mmHg), but has a viscosity of 28.53 cs at 100 ° C.
Of VI. The unhydrogenated lubricating oil product had a higher VI than the same viscosity oil produced from propylene over AlCl ₃ or BF ₃ catalysts as summarized.
The AlCl ₃ / HCl catalyst has an unhydrogenated lubricating oil yield of 87, a viscosity at 100 ° C. of 29.96 mm ² / s and a viscosity of 38.
The BF ₃ H ₂ O catalyst had an unhydrogenated lube yield of 23, a viscosity at 100 ° C. of 7.07 mm ² / s and a VI of 46.

The unhydrogenated lubricating oil product from the Cr / SiO ₂ catalyst has a C13-NM that is simpler than the acid-catalyzed lubricating oil.
Has an R spectrum.

Embodiment 3

The procedure of Example 2 was followed except that the reaction was carried out at 170 ° C., 2170-2860 kPa (300-4
00 psig). After 14 hours of reaction, 4
7.5 g of liquid and 18.4 g of gas (mainly propylene) were collected. The liquid product had the following composition as analyzed by gc. C ₆ (4.51), C ₉ (5.5
_{3), C 12 (5.01)} , C 15 ~C 20 (12.2
_{2), C 20 ~C 30 (} 5.30), C 30 + (6
7.43) (% by weight).

160 ° C./13.3 kPa (0.1 mmH
The unhydrogenated lubricating oil fraction after distillation excluding the light g) had a viscosity at 100 ° C. of 39.85 and a VI of 81.

Embodiment 4

A Cr / SiO ₂ catalyst was prepared as described in Example 1.

In a tubular reactor filled with 3 g of 1% Cr on silica catalyst, 5 g / h of propylene and 1.13 g / h of ethylene (C ₃ / C ₂ molar ratio = 3) were added at 190 ° C. and 1480 ° C. 2172 kPa (200 to 300 psig)
Supplied with The weight of the liquid product is 68 after 15 hours of distribution.
g. The single stream liquid yield was 75%.
The gas contains ethylene and propylene, which can be recycled. The liquid product was centrifuged to remove small amounts of solid particles. The clear liquid is fractionated to 50% of 1.33k
A light fraction boiling below 145 ° C. at Pa (0.01 mmHg) and 50% unhydrogenated lubricating oil product was obtained. The unhydrogenated lubricating oil product has a viscosity at 100 ° C. = 46.
03 mm ² / s (cS), viscosity at 40 ° C. = 703.25
mm ² / s (cS) and VI = 112. The light fraction is an unsaturated olefinic hydrocarbon having 6 to 25 carbon atoms. IR indicated the presence of an internal and vinylidene double bond. These olefins can be used as raw materials for the synthesis of other value-added products such as detergents, lubricating oils or fuel additives. These light fractions can also be used as gasoline or distillate.

This example shows that an activated Cr catalyst on silica can produce a lubricating oil with a high VI from a mixture of ethylene and propylene. Light products are useful as chemicals or fuels.

Embodiment 5

The experiment of Example 2 was continued for another 23 hours,
8 g of liquid product was collected. Single stream liquid yield 54%
Met. The liquid product was centrifuged to remove solid precipitate. The clear product is fractionated to give 35% of 1.33
A light fraction boiling at 145 ° C. or lower at kPa (0.01 mmHg) and a viscous unhydrogenated lubricating oil product of 65% were obtained. The unhydrogenated lubricating oil product has a viscosity at 100 ° C. = 7
2.40 mm ² / s (cS), viscosity at 40 ° C. = 980.
73 mm ² s (cS) and VI = 144.

Embodiment 6

The reactor, propylene and ethylene feed rates were the same as in Example 4. Further, n-octane was supplied as a solvent at 10 ml / hour to the reactor. After 17 hours of flow, 228 g of liquid product was collected. Mass balance indicated that all the ethylene propylene had been converted to the liquid product. The trace liquid after filtration of the solid was fractionated to give four fractions. Fraction 1 weighs 118 g at a boiling point of 130 ° C. or lower and is mainly an n-octane solvent, and fraction 2 has a boiling point of 123 ° C. or lower / 1.33.
It is 32 g at kPa (0.01 mmHg), and the fraction 3 is 170 ° C. or less / 1.33 kPa (0.01 mHg).
mHg) and fraction 4 was 40 g residual product. Fraction 4 has a viscosity at 100 ° C. = 30.99 mm ² / s (cS) and a viscosity at 40 ° C. = 3
It has a viscosity measurement of 43.44 mm ² / s (cS) and VI = 126.

This example shows that the presence of an inert solvent is advantageous for producing a low viscosity lubricating oil. The presence of the inert solvent also prevents the reactor from clogging due to the formation of traces of solids.

Embodiment 7

This example illustrates the production of a polypropylene liquid product using both a reduced metal catalyst (Example 7A) and a Ziegler catalyst (Example 7B).

Example 7A

The activated chromium on silica catalyst (15 g) and purified n-decane (400 ml) were charged to a 1 liter autoclave with stirring under a nitrogen atmosphere. When the temperature of the autoclave reached 160 ° C., liquid propylene was fed at 50 ml / h until 375 ml had been introduced into the reactor. After 16 hours at 160 RC, the slurry product was removed and filtered to remove the solid catalyst, 1.33 kPa
Distillation was performed within 120 ° C. under a vacuum of (0.01 mmHg) to remove light substances. The product yields and properties are summarized in Table 2.

Example 7B

Production of polypropylene liquid product with Ziegler catalyst ZrCp2Cl2 / MAO

A solution catalyst containing 0.17 mmol of zirconocene dichloride and 88 mmol of methylaluminoxane in 150 ml of toluene was charged to a 1 liter autoclave at 25 ° C. Propylene was fed at 50 ml / h until 375 ml was introduced into the reactor. After 16 hours, the catalyst components were deactivated by adding 1 ml of water.
The liquid product was isolated by drying and filtering off the solid components. The lubricating oil product was isolated as in Example 7A. The product yields and properties are summarized in Table 2 below.

The structure of the polymer formed by the use of a chromium catalyst is uniquely irregular. The C13 NMR spectra of these two examples showed that the chromium product of Example 7A was much less irregular than the Ziegler product of Example 7B. This regio irregularity is C-13
It can be determined by 2 / 4J INEPT (non-reactive nucleation strengthening by polarization transfer) NMR technique. Example 7A
The INEPT spectra of the products of 7 and 7B showed different types of methine carbon in the backbone of the chromium and Ziegler products.

The data in Table 2 show that when cracked at 280 ° C. under a nitrogen atmosphere for 24 hours, it had better thermal stability than the regular Ziegler product.

Embodiment 8

Preparation of poly-1-butene liquid product using reduced metal catalyst (Example 8A) and Ziegler catalyst (Example 8B)

Example 8A

[0063] Poly-1-butene was produced in a continuous downflow fixed bed reactor. The reactor consisted of a 9.5 mm (3/8 inch) outer diameter stainless steel tube. The bottom of the reactor contained 18 g of clean 14/20 mesh quartz chips supported on a 6 mm diameter coarse frit.
3 g of activated chromium catalyst was placed in the tube. The top of the reactor was filled with quartz chips that served as feed preheat. The reactor tube was covered with a thermally conductive jacket. The reactor temperature (125 ° C.) was measured and controlled by a thermocouple in the middle of the jacket. The 1-butene liquid is equi-volume Deox and 13 to remove oxygenates and water inclusions.
Pumped through a 50 ml Hoke bomb filled with X molecular sieve. 1-butene was fed to the reactor from the top. The reactor pressure [2310 kPa (320 psi)
g)] was controlled by a groove loader at the outlet of the reactor. The eluate is collected at the bottom of the reactor and the lubricating oil product is
Isolated by distillation within 140 ° C. under a vacuum of 3.3 kPa (0.1 mmHg). The properties of the product are summarized in Table 2.

Example 8B

Preparation of poly-1-butene liquid product over Ziegler catalyst ZrCp2Cl2 / MAO

The product was prepared as in Example 7B, except that 1-butene was used as the feed. The product yields and properties are summarized in Table 2.

C1 of the two products of Examples 8A and 8B
The 3 NMR spectrum shows that the chromium product of Example 8A is much less regular than the Ziegler product of Example 8B, by comparison with spectra reported in the literature for Ziegler polymers. The data in Table 2 show that the chromium product of Example 8A had better thermal stability than the regular Ziegler product of Example 8B when cracked at 280 ° C. under a nitrogen atmosphere for 24 hours.

Embodiment 9

Preparation of Ethylene / Propylene Copolymer Using Reduced Metal Catalyst and Ziegler Catalyst Example 9A

Same as Example 7A, except that gaseous ethylene (25.2 g / h) and propylene (25 g / h
) At 185 ° C. simultaneously into the autoclave. The product yields and properties are summarized in Table 2.

Example 9B

Preparation of ethylene / propylene copolymer liquid product with Ziegler catalyst ZrCp2Cl2 / MAO

Same as Example 7B, except that ethylene (25.2 g / h) and propylene (25 g / h)
It was fed simultaneously to the autoclave at 0 ° C.

The product yields and properties are summarized in Table 2.
The C13 NMR spectrum of the product shows that the chromium product of Example 9A is much less regular than the Ziegler product of Example 9B.

[0076]

[Table 2]

Embodiment 10

The liquid polypropylene product was prepared according to Example 7A.
The autoclave was heated to 80 ° C. using a metal catalyst that was reduced in the same manner as described above. The product yields and properties are summarized in Table 3 below.

Embodiment 11

A liquid ethylene / propylene copolymer was prepared as described in Example 10, except that ethylene (16.7 g / h) and propylene (25 g / h)
Simultaneously fed to the autoclave at 5 ° C. The product yields and properties are summarized in Table 3 below.

[0076]

[Table 3]

The estimated regio-irregularities of these products along with the reported data from the products obtained with Ziegler catalysts are summarized in Table 4.

[0078]

[Table 4]

These results show that chromium-catalyzed ethylene / propylene oligomers have a much greater amount of regio-irregularity than other catalyzed products. These unique structural features are related to their better thermal stability as indicated above.

An ethylene / C ₃ -C ₅ olefin
Gomer can be used as a blend component with mineral oil or low viscosity synthetic lubricants to improve viscosity and VI. The results of blending with mineral or synthetic oils are summarized in Table 5 below. As the examples of these blends show, the products of Examples 10 and 11 improve oil viscosity and VI. The products of Examples 10 and 11 have low molecular weights, in the thousands range, and can therefore be expected to have much better shear stability than similar polymers of high molecular weight.

[0081]

[Table 5]

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

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C07B 61/00 300 C07B 61/00 300 C10N 20:02 70:00 (56) Reference US Pat. No. 4,969,732 (US, A) U.S. Pat. No. 4,962,249 (US, A) WO 89/12662 (WO, A1) WO 90/13620 (WO, A1) West German Patent Application 3427319 (DE, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 2/10 C07C 9/16 C07C 9/22 C10M 105/04 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (10)

(57) [Claims] 1. A C ₃ -C ₅ alpha - a mixture of olefins or ethylene and C ₃ -C ₅ alpha - and olefins
The mixture is brought to a pressure of 10 to 34600 kPa and 0 to 25
A chromium catalyst on a porous support, at a reaction temperature of 0 ° C., in the presence of an oxidizing gas at 200 to 900 ° C.
At a temperature of at least 20% by weight and then contacting the catalyst treated with a reducing agent at a temperature and for a time sufficient to reduce the chromium of the catalyst to a lower valence state by at least 20 mol%
A method for producing a lubricant base material , wherein a liquid olefin oligomer having irregularity is produced. 2. The process of claim 1 including the additional step of hydrogenating the resulting liquid olefin oligomer or fraction thereof to convert it to a saturated hydrocarbon. 3. A mixture of alpha-olefins comprising predominantly propylene and ethylene present in a molar ratio of propylene to ethylene of from 10 to 1: 1.
the method of. 4. The process according to claim 1, wherein the reaction temperature is between 90 and 250 ° C. 5. A reducing agent comprising carbon monoxide, having an oligomerization temperature of 100 to 200 ° C. and a pressure of 790 to 200 ° C.
170 kPa and a viscosity at 100 ° C. of 35 mm ² /
2. The yield of products greater than s greater than 35%.
5. The method according to any one of the items 4 to 4. 6. The method according to claim 1, wherein the porous support comprises silica. 7. The produced liquid olefin oligomer is
7. The method according to claim 1, comprising at least 40% by weight of oligomers in the lubricant range having at least 30 carbon atoms. 8. Mixture of C ₃ -C ₅ alpha-olefins
Things or C ₃ -C ₅ alpha - Group VIB of reduced valence state mixture on a porous support of an olefin and ethylene
An oligomer product obtained by contacting with an oligomerization catalyst comprising a Group III metal catalyst, wherein the product comprises at least 2
Lubricant base material with 0 mole% regio disorder . 9. The liquid composition according to claim 8, wherein the regio irregularity is 20 to 60%. 10. The method of claim 1, wherein the oligomer product comprises at least one
Species C ₃ -C ₅ alpha - liquid composition of claim 9 which is the oligomerization product of mixing <br/> compound of olefins with ethylene.