MXPA01005116A - Oligomer oils and their manufacture - Google Patents

Abstract

A multistep process for the selective production of an oligomer oil having predetermined properties in which the first step involves the polymerization of a feedstock containing one or more C3 to C20 1-olefins in the presence of a catalyst comprising a bulky ligand transition metal catalyst and in which a subsequent step involves the oligomerization of at least a preselected fraction of the product of the first step.

Description

ORIGINAL OILS AND ITS MANUFACTURE BACKGROUND OF THE INVENTION Field of the Invention The present invention relates generally to a multistage preparation of an oligomer oil, and relates more particularly to a preparation of the aforementioned several steps in which the first step involves polymerization of a feedstock containing one or more C3 to C20 1-olefins in the presence of a catalyst comprising a bulky ligand transition metal catalyst and in which a subsequent step involves the oligomerization of at least one preselected fraction of the product of the first stage.

Discussion of the Prior Art Numerous processes have been described for polymerizing or oligomerizing an ethylenically unsaturated olefin. For example, Rossi et al., PCT / US93 / 12102, published June 23, 1994 as WO 94/13715, describe a catalyst system comprising a bulky ligand transition metal compound having a formula corresponding very much to close to REF: 128994 Formulas 1, 2 or 3 or 4 below. The catalyst system also includes an activating compound containing a Group II or III metal of the Periodic Table of the Elements, especially trialkylaluminum compounds, both linear and cyclic alumoxanes, or ionizing ionic activators or compounds such as tri (n-butyl) ammonium tetra (penta-fluorophenyl) boron. The process described involves copolymerization of ethylene and an alpha-olefin. Suitable alpha-olefins have a hydrogen atom in the second carbon, at least two hydrogens in the third carbon or at least one hydrogen in the fourth carbon. The resultant copolymers produced contain a high degree of ethenylidene or terminal vinylidene unsaturation, and have a number average molecular weight of 300 to 15,000 and a molecular weight distribution (M "/ Mn) of typically less than 5. Bagheri et al. ., U.S. Patent No. 5,688,887 describe another process for polymerizing a feedstock containing one or more C3 to C2o 1-olefins and a second hydrocarbon that is not a 1-olefin, to form a poly (1-) olefin) or copol i (1-olefin) containing essentially viscous, low molecular weight, highly reactive 1-olefin in the presence of a metallocene catalyst comprising a metallocene catalyst of Group IVb Periodic cyclopentadienyl or indenyl and a cocatalyst of aluminoxane The resulting polymer product has a terminal vinylidene content of more than 80%, is highly reactive and has a molecular weight between 300 and 10,000. Bagheri et al. Also describe reactions of the poly (1-olefin) product or copoly (1-olefin) in which the terminal vinylidene linkage is reacted with an aromatic product, an epoxidation agent, a silylating agent, maleic anhydride, carbon monoxide and hydrogen, halogen and hydrohalogen. Johnson et al., PC / US 96/01282, published August 1, 1996 as WO 96/23010, disclose processes employing a catalyst system comprising a different type of bulky ligand transition metal compound having a formula which corresponds closely to Formulas 5, 6, 7 or 8 below. The processes described involve the use of the aforementioned catalyst for the polymerization of ethylene, acyclic olefins and / or selected cyclic olefins and optionally selected olefinic esters or carboxylic acids, and other monomers to produce a wide variety of homopolymers and copolymers.

In addition, there have been a number of patent publications disclosing a catalyst system comprising a bulky ligand transition metal compound having a stoichiometric formula which is similar to that of Formula 9 or 10 below and an activating amount of a selected activator of organoaluminum compounds and hydrocarbylboro compounds. For example, Britovsek et al., PCT / GB98 / 02638, published March 18, 1999 as WO 99/12981, describe a catalyst system for use in the polymerization of 1-olefins. Brookhart et al., PCT / ÜS98 / 00316, published July 16, 1998 as WO 98/30612, describe a similar catalyst system for use in the polymerization of propylene. Brookhart et al., PCT / US98 / 14306, published January 21, 1999 as WO 99/02472, describe a process for producing alpha-olefins by reacting ethylene in the presence of a similar catalyst system and describing that the alpha-olefins produced they can also be homopolymerized or copolymerized with other olefins to form polyolefins or can be converted to alcohols. Bennett, PCT / US97 / 23556, published June 25, 1998 as WO 98/27124, describes a process for polymerizing ethylene in the presence of a similar catalyst system. Vaughn et al., PCT / US97 / 10418, published December 24, 1997 as WO 97/48736, describe a process for heterogeneously polymerizing an olefin monomer in the presence of a similar catalyst system comprising a transition metal compound of voluminous ligand immobilized in a support material. Matsunaga et al., PCT / US97 / 10419, published December 24, 1997 as WO 97/48737, discloses a process for homopolymerizing or copolymerizing ethylene in the presence of a catalyst system at elevated ethylene pressures. A major problem associated with the manufacture of vinyl olefin oligomer oils is that the mixture of the oligomer product must be fractionated in different portions to obtain oils of a desired viscosity produced (eg, 2, 4, 6 or 8 cSt at 100). ° C). As a result, in commercial production it is difficult to obtain a mixture of the oligomer product which, when fractionated, produces the relative quantities of each product of viscosity corresponding to the market demand, and is often necessary to produce an excess of a product. to get the amount needed from the other. Another problem is the lack of control over the chemistry, and the isomerization of alpha olefins to internal olefins. A third problem is that polymerization processes often produce a high percentage of dimer, which is inadequate (too volatile) for use as a lubricant. Therefore, it is highly desirable to develop a process that provides the versatility to allow the viscosity of the product to be adapted with improved selectivity and product oils having a preselected desired viscosity that are reproducible and easily manufactured. Schaerfl et al., U.S. Patent Nos. 5,284,988 and 5,498,815 disclose two two-stage processes for preparing a synthetic oil that produces improved versatility to allow an adaptation of the viscosity of the synthetic oil product with improved selectivity. U.S. Patent No. 5,284,988 describes a process that provides improved selectivity when shaped synthetic oils are used as starting olefins, vinylidene olefins and alpha olefins. The process of U.S. Patent No. 5,284,988 for manufacturing a synthetic oil comprises (a) isomerizing at least a portion of a vinylidene olefin feed in the presence of an isomerization catalyst to form an intermediate containing tri-substituted olefin and (b) codimerizing the intermediate and at least one vinyl olefin in the presence of an oligomerization catalyst to form a synthetic oil comprising a co-dimer of the vinylidene olefin and the vinyl olefin. Suitable vinylidene olefins for use in the isomerization stage of the process of U.S. Patent No. 5,284,988 can be prepared using known methods such as by dimerization of vinyl olefins containing from 4 to about 30 carbon atoms, preference at least 6, and more preferably at least 8 to about 20 carbon atoms, including mixtures thereof. Vinyl olefins suitable for use in the codimerization step of the process of U.S. Patent No. 5,284,988 contain from 4 to about 30 carbon atoms, and, preferably from about 6 to about 24 carbon atoms, including mixtures thereof. The codimerization step can utilize any suitable dimerization catalyst known in the art and especially Friedel-Crafts type catalysts such as acid halides (Lewis acid) or protonic acid catalysts (Bronsted acid), which can be used in combination and with promoters. U.S. Patent No. 5,498,815 discloses a process for manufacturing a synthetic oil comprising the steps of reacting an olefin of vinylidene in the presence of a catalyst to form an intermediate mixture containing at least about 50 weight percent of dimer of the vinylidene olefin, and thereafter add a vinyl olefin to the intermediate mixture and react the intermediate mixture and the vinyl olefin in the presence of a catalyst to form a product mixture containing the vinylidene olefin dimer and a co-dimer of the vinyl olefin added with the vinylidene olefin. The vinylidene olefins suitable for use in the first step of this process can be prepared using known methods, such as by dimerization of vinyl olefins containing from 4 to about 30 carbon atoms. The vinyl olefins suitable for use in the second stage of this process contain from 4 to about 30 carbon atoms. Both stages can utilize any suitable dimerization catalyst known in the art and especially Friedel-Crafts type catalysts such as acid halides (Lewis acid) or protonic acid catalysts (Bronsted acid), whose catalysts can be used in combination and with promoters. Hobbs et al., PCT / US90 / 00863, published September 7, 1990 as WO 90/10050, describe a method for improving the thermal stability of synthetic lubricants composed of alpha-olefin oligomers by alkylation, thereafter in the presence of an acid alkylation catalyst with an olefin such as decene or the olefins classified as non-lubricating, low molecular weight produced in the course of the oligomerization of 1-alkenes. The alpha-olefin oligomers are obtained by the oligomerization of the alpha-olefin feedstock from Ce to C20 in the presence of a metal catalyst of Group VIB at reduced valence state on a porous support and by recovering the oligomers of the resulting product mixture comprising hydrocarbons classified as olefinic lubricant. However, neither U.S. Patent No. 5,284,988, nor U.S. Patent No. 5,498,815, nor PCT / US 90/00863 disclose a multi-stage process which involves in the first stage the polymerization of an olefin in presence of a catalytic system comprising a bulky ligand transition metal complex to form a product mixture comprising a product distribution of at least one fraction having properties that are outside a predetermined classification, and a subsequent stage of the oligomerization of at least one preselected fraction of the product mixture formed in the first stage.

Object of the Invention It is therefore a general object of the present invention to provide an improved process for producing an oligomer oil having predetermined properties that overcomes the aforementioned problems of the above methods. More particularly, it is an object of the present invention to provide a previously mentioned improved process that allows a greater degree of control over the chemistry and minimizes the degree of double bond isomerization of the olefins in the feedstock.

It is a related object of the present invention to provide an aforementioned improved process that allows for improved efficiency in the conversion of ethylene olefins to oligomer oils having predetermined properties. Other objects and advantages will become apparent upon reading the following detailed description and appended claims.

Brief Description of the Invention These objects are achieved by the process of the present invention for the selective production of an oligomer oil having predetermined properties comprising a first step (a) of polymerizing a feed comprising one or more olefins of C3 to C2o having at least one hydrogen on the 2 carbon atoms, at least two hydrogens on the 3 carbon atoms and at least one hydrogen on the 4 carbon atoms (if at least 4 carbon atoms are present in the olefin), in the presence of a catalyst system comprising a bulky ligand transition metal complex of Formula 1 and an activating amount of an activator comprising an organoaluminum compound or a hydrocarbylboro compound or a mixture thereof: Formula 1 LmMXnX p in Formula 1, L is the bulky ligand, M is the transition metal, X and X1 may be the same or different and are independently selected from the group consisting of halogen, hydrocarbyl group or hydrocarboxyl group having 1-20 carbon atoms , m is 1-3, n is 0-3, p is 0-3 and the sum of the integers m + n + p corresponds to the valence of the transition metal. A product mixture is formed comprising a product distribution of at least one fraction having properties that are outside of a predetermined classification thereof. In a subsequent step (b), at least one preselected fraction of the product formed in step (a) is oligomerized in the presence of an acid oligomerization catalyst to thereby form the aforementioned oligomer oil.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The catalyst system employed in step (a) of the method of this invention comprises a bulky ligand transition metal complex of the stoichiometric Formula 1: Formula 1 LmMXnX p wherein L is the bulky ligand, M is the transition metal, X and X1 are independently selected from the group consisting of halogen, hydrocarbyl group or hydrocarboxyl group having 1-20 carbon atoms, and m is 1-3, n is 0-3, p is 0-3, and the sum of the integers m + n + p corresponds to the valence of transition metal. The aforementioned metal complex contains a multiplicity of linked atoms that form a group that can be cyclic with one or more optional heteroatoms. Ligands L and X may be bridged together, and if two ligands L and / or X are present, they may be in bridge form. In a preferred embodiment, the catalyst is a metallocene, M is a transition metal of Group IV, V or VI, and one or more of L is a cyclopentadienyl or indenyl portion. In this embodiment, the feed comprises one or more linear C3 to C20 1-olefins, and the product mixture formed in step (a) comprises a poly (1-olefin) or copoly (1-olefin) which contains essentially 1 -olefin, viscose, essentially in unsaturated terminal form with molecular weight between 300 and 10,000 having a terminal vinylidene content of more than 50%, preferably more than 80%. The metallocene is preferably represented by the stoichiometric Formula 2: Formula 2 (Cp) pMR'nR2, wherein each Cp is a substituted or unsubstituted cyclopentadienyl or indenyl ring, and each substituent may next be the same or different and is an alkyl, alkenyl, aryl, alkaryl or aralkyl radical having from 1 to 20 carbon atoms or at least two carbon atoms formed together to form a part of a C4 or C6 ring; wherein R1 and R2 are independently selected from the group consisting of halogen, hydrocarbyl, hydrocarboxyl, each having 1-20 carbon atoms; and where m is 1-3, n is 0-3, p is 0-3, and the sum of m + n + p corresponds to the oxidation state of M.

In alternative preferred embodiments, the metallocene is represented by the stequio-metric Formulas 3 or 4: Formula 3 (C5R3g) kR4s (C5R g) MQ3_k.x Formula 4 R'SÍCSR? MQ1 wherein each C5R g is a substituted or unsubstituted cyclopentadienyl, wherein each R3 may be the same or different and is hydrogen, alkyl, alkenyl, alkaryl or aralkyl having from 1 to 20 carbon atoms or at least 2 carbon atoms attached together to form a part of a ring from C to C6; wherein R4 is either 1) an alkylene radical containing from 1 to 4 carbon atoms, or 2) a dialkylgermanium or silica radical or an alkyl phosphoric or amine radical, and R4 is a substituent on and bridge of two. C5R3g rings or bridge of a ring of CsR3g subsequent to M, wherein each Q may be the same or different and is an alkyl, alkenyl, aryl, alkaryl or arylalkyl radical having from 1 to 20 carbon atoms or halogen, and Q r is an alkylidene radical having from 1 to 20 carbon atoms; when k is 0, x is 1, otherwise x is always 0; and where s is 0 or 1; and when s is 0, g is 5 and k is 0, 1 or 2; and when s is 1, g is 4 and k is 1. M is a transition metal of Group IV, V or VI, preferably Group IV. In another preferred embodiment, the catalyst, instead of being a metallocene, is a stoichiometric Formula 5, 6, 7 or 8 complex having a bidentate ligand: Formula 5 Formula 6 Formula 7 Formula 8 In Formulas 5-8, the transition metal M is selected from the group consisting of Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd; X and X1 are independently selected from the group consisting of halogen, hydrocarbyl group, and hydrocarboxyl group having from 1 to 20 carbon atoms; n and p are integers whose sum is the valence of M minus 2 (the number of bonds between M and the bidentate ligand), R5 and R8 are each independently hydrocarbyl or substituted hydrocarbyl, with the proviso that the carbon atom attached to the atom of imino nitrogen has at least two carbon atoms attached to it; R6 and R7 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R6 and R7 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring; R9 and R12 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R10 and R11 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R15 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or two of R15 taken together form a ring; R16 is hydrocarbyl or substituted hydrocarbyl; and R13 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R16 and R13 taken together form a ring; R17 is hydrocarbyl or substituted hydrocarbyl, and R, 1x4 * is hydrogen, hydrocarbyl or substituted hydrocarbyl, or R117 'and R, 114 * taken together form a ring; each R18 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R19 and R22 are each independently hydrocarbyl or substituted hydrocarbyl, with the proviso that the carbon atom attached to the imino nitrogen atom has at least two carbon atoms attached thereto; R20 and R21 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R23 is independently hydrocarbyl or substituted hydrocarbyl with the proviso that any olefinic bond in the olefin is separated from any other olefinic or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms. When M is Pd, no diene is present, and when a complex of Formula 5 is used, M is not Pd. M is preferably Co, Fe, Ni or Pd; and Ni or Pd is more preferred. In Formula 7, n is 2 or 3. In another preferred embodiment, instead of being a metallocene or a complex involving a bidentate ligand, the aforementioned bulky ligand transition metal complex is a complex of Stoichiometric Formula 9: Formula 9 wherein three nitrogen atoms N1, N2 and N3 are co-ordinated to the transition metal M selected from Co, Fe, Ru and Mn; wherein G comprises one or more organic portions to which the three nitrogen atoms N1, N2 and N3 are collectively or separately bound; wherein X and X1 are independently selected from the group consisting of halogen, hydrocarbyl group and hydrocarboxyl group having 1 to 20 carbon atoms; where n and p are integers whose sum is the valence of M minus 3 (the number of links between M and the tridentate ligand); and where M is Co, when the sum of the integers n and p is 1, 2, or 3, when M is Ru, the sum of n and p is 2, 3 or 4, when M is Fe, the sum of n and p is 2 or 3, and when M is Mn, the sum of n and p is 1, 2, 3 or 4. In a highly preferred embodiment of the complex of Formula 9, the aforementioned metal complex has the structure of Formula 10: Formula 10 wherein M is Fe [II], Fe [III], Co [I], Co [II], Co [III], Ru [II], Ru [IV], Mn [I], Mn [II], Mn [III] or Mn [IV]; wherein X and X1 are independently selected from the group consisting of halogen, hydrocarbyl group and hydrocarboxyl group having from 1 to 20 carbon atoms where n and p are integers whose sum is the valence of M; wherein R24, R25, R26, R27 and R29 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and wherein (1) when M is Fe, Co or Ru, R28 and R30 are independently selected of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and when any two or more of R24-R30 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, the two or more may be linked to form one or more substituents cyclic, or (2) when M is Fe, Co, Mn or Ru, then R28 is represented by the stoichiometric Formula 11, and R30 is represented by the stoichiometric Formula 12 as follows: Formula 11 Formula 12 wherein R a R are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and wherein any two or more of R24 to R27, R29 and R31 to R40 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, the two or more may be linked to form one or more cyclic substituents; with the proviso that at least one of R31, R32, R33 and R34 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems of Formulas 11 or 12 are part of a polyaromatic fused ring system, or (3) when M is Fe, Co, Mn or Ru, then R28 is a group having the formula -NR 1R42 and R30 is a group having the formula -NR43R44, wherein R41 to R44 are independently selected from hydrogen, halogen , hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and where when any of two or more from R24 to R27, R, 2"9 R R, 4 f4 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more may be attached to form one or more cyclic substituents.

In addition to the bulky ligand transition metal complex, the catalyst system employed in step (a) of the method of this invention also contains an activating amount of an activator selected from organoaluminium compounds and hydrocarbylboro compounds. Suitable organoaluminum compounds include compounds of the formula A1R503, when each R50 is independently C alquilo-C? 2 alkyl or halo. Examples include trimethylaluminum (TMA), triethylaluminum (TEA), tri-isobutylaluminum (TIBA), t-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride, methylaluminum sesquichloride, and alumoxanes. Alumoxanes are well known in the art and usually oligomeric compounds that can be prepared by the controlled addition of water to an aluminum alkyl compound, for example trimethylaluminum. Such compounds may be linear, cyclic or mixtures thereof. Commercially available alumoxanes are usually created to be mixtures of linear or cyclic compounds. The cyclic alumoxanes can be represented by the formula [R 51A; 10) the linear alumoxanes by the formula R52 (R53A10) S wherein s is a number from about 2 to 50, and wherein R51, R52, and R53 represent hydrocarbyl groups, preferably Ci to C6 alkyl groups, e.g. methyl, ethyl or butyl. Alkylalumoxanes such as methylalumoxane (MAO) are preferred. Mixtures of alkylalumoxane and trialkylaluminum compounds are particularly preferred, such as MAO with TMA or TIBA. In this context it should be noted that the term "alkylalumoxane" as used in this specification includes commercially available alkylalumoxanes which may contain a proportion, usually about 10 weight percent, but optionally up to 50 weight percent, of the corresponding trialkylaluminium, for example, commercial MAO usually contains about 10 weight percent trimethylaluminum (TMA), while commercial MMAO contains both TMA and TIBA. The amounts of alkylalumoxane mentioned herein include such trialkylaluminium impurities, and accordingly the amounts of trialkylaluminum compounds cited herein are considered to comprise additional compounds of the formula A1R3 for any compound of A1R3 incorporated within the alkylalumoxane when present .

Examples of suitable hydrocarbyl boron compounds are boroxines, trimethylboro, triethylboron, dimethylphenylammonium tetra (phenyl) borate, trityl tetra (phenyl) borate, triphenylboron, dimethylphenylammonium, tetra (pentafluorophenyl) borate, tetrakis [(bis-3,5-trifluoromethyl) ) phenyl] borate sodium, trityl tetra (penta-fluorophenyl) borate and tris (pentafluorophenyl) -boron. In the preparation of the catalysts of the present invention, the amount of activating compound selected from organoaluminum compounds and hydrocarbylboro compounds that is employed is easily determined by simple testing, for example, by the preparation of small test samples that can be used to polymerize small amounts of the monomer or monomers and to thereby determine the activity of the catalyst produced. It is generally found that the amount employed is sufficient to provide from 0.1 to 20,000 atoms, preferably from 1 to 2000 atoms, of aluminum or boron per atom of the transition metal in the compound of Formula 1. Generally, from about 1 mole to about 5000 moles, preferably about 150 moles of activator are employed per mole of transition metal complex.

When the catalyst system employed in step (a) of the method of this invention comprises a complex of Formulas 5-12, the catalyst preferably comprises a neutral Lewis Base in addition to the bulky ligand transition metal complex and the activator . Neutral Lewis bases are well known in the art of Ziegler-Natta catalyst polymerization technology. Examples of Lewis base classes nutrated suitably employed in the present invention are unsaturated hydrocarbons, for example alkenes (other than 1-olefins) or alkynes, primary, secondary and tertiary amines, amides, phosphoramides, phosphines, phosphites, ethers, thioethers, nitriles, carbonyl compounds, eg, esters, ketones, aldehydes, carbon monoxide and dioxide carbon, sulfoxides, sulfones and boroxines. Although the 1-olefins are capable of acting as neutral Lewis bases, for the purposes of the present invention they are considered to be 1-olefins of monomer or comonomer and not as neutral Lewis bases per se. However, alkenes which are internal olefins, for example, 2-butene and cyclohexene are considered as neutral Lewis bases in the present invention. Preferred Lewis bases are tertiary amines and aromatic esters, for example, dimethylaniline, diethylaniline, tributylamine, ethyl benzoate and benzyl benzoate. In this particular embodiment of the present invention, the transition metal complex (first component), the activator (second component), and the neutral Lewis base (third component) of the catalyst system can be conducted together simultaneously or in any desired order . However, if the aforementioned second and third are compounds that interact firmly together, for example, form a stable compound together, it is preferred to conduct them together either the aforementioned first and second components or the aforementioned first and third components in one step initial before entering the final defined component. Preferably, the first and third components are brought into contact together before the second component is introduced. The amounts of the first and second components used in the preparation of this catalyst system are suitably as described above with respect to the catalysts of the present invention. The amount of the neutral Lewis Base (component 3) is preferably such that it provides a neutral Lewis Base ratio to the first component of 100: 1 to 1: 1000, more preferably in the range of 10: 1 to 1 :twenty. The three components of the catalyst system can be conducted together, for example, as pure materials, as a suspension or solution of the materials in a suitable diluent or solvent (for example a liquid hydrocarbon), or, if at least one of the components is volatile, using the vapor of that component. The components can be driven together at any desired temperature. It is generally satisfactory to mix the components together at room temperature. Heating at higher temperatures, for example, up to 120 ° C, can be carried out if desired, for example, to achieve better mixing of the components. It is preferred to carry out the driving together of the three components in an inert atmosphere (eg, dry nitrogen) or in va cuo. If it is desired to use the catalyst on a support material (see below), this can be achieved, for example, by making the catalyst system comprising the three components and impregnating the support material preferably with a solution thereof, or by introducing one or more of the components simultaneously or sequentially into the support material. If desired, the support material itself may have the properties of a neutral Lewis base and may be employed as, or in lieu of, the aforementioned third component. An example of a support material having properties of the neutral Lewis base is poly (aminoes tyno) or a copolymer of styrene and tyrosine aminoes (ie vinylaniline). The catalysts of the present invention may, if desired, comprise more than one of the defined transition metal compounds. The catalyst may comprise, for example, a mixture of 2,6-diacetylpyridinbis (2,6-diisopropylanyl) FeCl 2 complex complex or 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2, or a mixture of 2, 6-diacetylpyridine (2,6-diisopropylanyl) CoCl 2 and 2,6-diacetylpyridinbis (2,4,6-trimethylanil) FeCl 2. In addition to one or more defined transition metal compounds, the catalysts of the present invention may also include one or more other types of transition metal compounds or catalysts, for example, transition metal compounds of the type used in systems conventional Ziegler-Natta catalysts, metallocene-based catalysts, or chromium oxide catalysts supported with activated heat (for example Phillips-type catalyst). The catalyst employed in the process of step (a) of the present invention may be unsupported or supported (absorbed or adsorbed or chemically bound) in a convenient conventional support material. Suitable solid particle carriers are usually comprised of polymeric or refractory oxide materials, each preferably being porous, such as, for example, talc, inorganic oxides, inorganic chlorides, for example magnesium chloride, and resinous support materials such as polystyrene, polyolefin, or other polymeric compounds or any other organic support material and the like having an average particle size preferably greater than 10 μm. Preferred support materials are inorganic oxide materials, which include those of the Periodic Table - of the Metal Elements, Groups 2, 3, 4, 5, 13 or 14 or metalloid oxides. In a preferred embodiment, the catalytic support materials include silica, alumina, silica-alumina and mixtures thereof. Other inorganic oxides which can be employed either alone or in combination with silica, alumina or silica-alumina are magnesia, titania, zirconia and the like. It is preferred that the support material has a surface area in the range of from about 10 to about 700 m2 / g, a pore volume in the range of from about 0.1 to about 4.0 cc / g, and an average particle size in the range of from about 10 to about 500 μm. More preferably, the surface area is in the range of from about 50 to about 500 m2 / g, the pore volume is in the range of from about 0.5 to about 3.5 cc / g, and the average particle size is in the range from about 20 to about 200 μm. Most preferred, the range of the surface area is from approximately 100 to approximately 400 m2 / g; the pore volume is from about 0.8 to about 3.0 cc /, and the average particle size is from about 30 to about 100 μm. The pore size of the carrier of the invention typically has a pore size in the range from 10 to about 1000 A, preferably from 50 to about 500 A and more preferably from 75 to about 350 A. The bulky ligand transition metal compound is deposited on the support generally at a loading level of 100 to 10 micromoles of the gram-transition metal compound of solid support; more preferably from 80 to 20 micromoles of transition metal compound to gram of solid support; and more preferably from 60 to 40 micromoles of transition metal compound to gram of solid support. While the bulky ligand transition metal compound can be deposited on the support at any level up to the pore volume of the support, loading levels of less than 100 micromoles of transition metal compound to gram of solid support are preferred, with less than 80 micromoles of transition metal compound to gram of solid support which is more preferred, and less than 60 micromoles of transition metal compound to gram of solid support which is most preferred. The impregnation of the support material can be carried out by conventional techniques, for example, by forming a solution or suspension of the catalyst components in a suitable diluent or solvent, or by fusing the support material therewith. The support material impregnated in this way with the catalyst can then be separated from the diluent, for example, by filtration or evaporation techniques. If desired, the catalysts can be formed in si tu in the presence of the support material, or the support material can be prepreg or premixed, simultaneously or sequentially, with one or more of the catalyst components. The formation of the support catalyst can be achieved, for example, by treating the transition metal compounds of the present invention with alumoxane in a suitable inert diluent, for example, a volatile hydrocarbon, by fusing a particulate support material with the product and evaporating the volatile diluent. The produced supported catalyst is preferably in the form of a fluid free powder. The amount of support material employed can vary widely, for example from 100,000 to 1 grams per gram of metal present in the transition metal compound. The polymerization conditions employed in step (a) of the method of this invention can be, for example, either in solution phase, suspension phase or gas phase and either batch, continuous or semi-continuous, with temperatures of polymerization ranging from -100 ° C to + 300 ° C. In the process of the suspension phase and in the gas phase process, the catalyst is generally fed to the polymerization zone in the form of a particulate solid. This solid can be, for example, an undiluted solid catalyst system formed of the bulky ligand transition metal complex employed in the method of the present invention and an activator, or it can be the solid complex alone. In the latter situation, the activator can be fed to the polymerization zone, for example as a solution, separately from or together with the solid complex. In the suspension phase polymerization process, the solid particles of the catalyst, or support catalyst, are fed to a polymerization zone either as a dry powder or as a suspension in the polymerization diluent. Preferably, the particles are fed to a polymerization zone as a suspension in the polymerization diluent. The polymerization zone may be, for example, an autoclave or similar reaction vessel, or a continuous loop reactor, for example of the type well known in the manufacture of polyethylene by the Phillips Process. Methods for operating the gas phase polymerization processes are well known in the art. Such methods usually involve stirring (for example by stirring, vibration or fluidization) a catalyst bed, or a bed of the target polymer (ie polymer having the same or similar physical properties for that which is desired to be made in the polymerization process) containing a catalyst, and feeding it a monomer stream at least partially in the gas phase, under conditions such that at least part of the monomer is polymerized in contact with the catalyst bed. The bed is generally cooled by the addition of cold gas (for example recirculated gaseous monomer) and / or volatile liquid (for example volatile inert hydrocarbon, or gaseous monomer that has been condensed to form a liquid). The polymer produced in, and isolated from, gas phase processes directly forms a solid in the polymerization zone and is free of liquid, or substantially free of liquid. As is well known to those skilled in the art, if any liquid is allowed to enter the polymerization zone of a gas phase polymerization process, the amount of liquid is small in relation to the amount of polymer present in the polymerization zone. . This is in contrast to the "solution phase" processes where the polymer dissolved in a solvent is formed, and "suspension phase" processes where the polymer is formed as a suspension in a liquid diluent. Step (a) of the present invention may be operated under batch, semi-batch or so-called "continuous" conditions by methods that are well known in the art. The polymerization process of step (a) of the method of the present invention is preferably carried out at a temperature above 0 ° C, more preferably above 15 ° C. The adjustment of the polymerization within those defined temperature ranges can provide a useful means to control the average molecular weight of the polymer produced. Monomers which are suitable for use as the olefin undergoing the reaction in step (a) of the process of the present invention are alpha-olefins having (1) at least one hydrogen on the 2 carbon atoms, (2) minus two hydrogens on the 3 carbon atoms, and (3) at least one hydrogen on the 4 carbon atoms (if at least 4 carbon atoms are present in the olefin). Thus, suitable alpha-olefin monomers include those represented by the formula H2C = CHR60 wherein R60 is a straight or branched chain alkyl radical comprising from 1 to 18 carbon atoms and wherein any branching which is present is in one or more carbon atoms that are not closer to the double bond than the 4 carbon atoms. R60 is an alkyl, preferably containing from 1 to 19 carbon atoms, and more preferably from 2 to 13 carbon atoms. Thus, useful alpha-olefins include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1- dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and mixtures thereof. Step (a) of the process of the present invention is controlled by making the polymer having a number average molecular weight of not more than 15,000 and usually from 300 to 15,000, and preferably from 400 to 8,000. The number average molecular weight of such polymers can be determined by any convenient known technique. A convenient method for such determination is by size exclusion chromatography (also known as gel permeation chromatography, CPG) which additionally provides molecular weight distribution information (see WW Yau, JJ Kirkland and DD Bly, "Modern Size Exclusion Liquid Chromatography ", John Wiley and Sons, New York, 1979). The molecular weight distribution (Mw / Mn) of the polymers or copolymers produced in step (a) is usually less than 5, preferably less than 4, more preferably less than 4, for example between 1.5 and 2.5. When the catalyst of Formula 2, 3 or 4 is employed, the polymers produced in step (a) of this invention are further characterized in that up to about 50% or more of the polymer chains possess terminal ethylenylidene type initiation. A smaller amount of the polymer chains may contain terminal vinyl unsaturation, ie, POLY-CH = CH2, and a proportion of the polymers may contain internal monounsaturation, eg, POLY-C (T1) = CH (T2), wherein T1 and T2 are each independently an alkyl group containing from 1 to 18, preferably at 8 carbon atoms and POLY represents the polymer chain. The polymer products of step (a) of this inventive process comprise chains that can be saturated by hydrogen, but preferably contain polymer chains wherein at least 50, preferably at least 60, and most preferably at least 75 per hundred (for example, 7-5-98%), of which it has the presence of terminal ethenylidene (vinylidene). The percentage of polymer chains exhibiting terminal ethenylidene instalation can be determined by Fourier Transform Infrared (FTIR) spectroscopic analysis, titration, NMR (H) or proton NMR13C. In a preferred embodiment, step (a) is conducted under solution phase conditions using a catalyst system comprising a catalyst of Formula 2, 3 or 4, wherein M is a transition metal of Group IVb, typically titanium, zirconium or hafnium, and aluminoxane as an activator with the molar ratio of aluminoxane to metallocene of 150 or greater, and the alpha-olefins of C3-C20 in a feedstock containing more than 1 weight percent of at least one liquid of volatile hydrocarbon but consisting essentially of the C3-C20 alpha-olefins, are polymerized to form a poly (1-olefin or copoly (1-olefin) containing essentially 1-olefin, viscous, essentially terminally unsaturated, which it has a terminal vinylidene content of more than 50% In this preferred embodiment, the viscous, unsaturated polymer product of this invention is essentially a poly (1-olefin) or copoly (1-olefin). The polymer of the viscous polymers produced in step (a) of the method of this invention are essentially terminally unsaturated. By essentially terminally unsaturated it is meant that preferably less than about 90% of the polymer chains contain unsaturation, more preferably more than about 95% of the polymer chains in the product polymer contain terminal unsaturation. When a catalyst of Formula 5, 6, 7 or 8 is employed, the polymers produced in step (a) of this invention are further characterized, followed by the removal of light polymers (< C26), having a viscosity between and 200 cSt, a viscosity index between 110 and 230, a pour point less than -20 ° C, and a volatility of Noack at 250 ° C between 1% and 20%. In general, the products produced in step (a) are mixtures whose components and their relative amounts depend on the particular alpha-olefin reagent, the catalyst and the reaction conditions employed. Typically, the products are unsaturated and have viscosities ranging from about 2 to about 100 cSt at 100 ° C. At least a portion of the product mixture has the desired properties, for example, viscosity, for a particular application. The components in such a portion are usually hydrogenated to improve their oxidation resistance and are known for their superior properties of long life, low volatility, runoff temperatures and high viscosity indexes, which make them a main base material for lubricants and hydraulic fluids. of the state of the art. However, usually such a product mixture includes substantial amounts of unreacted olefin feed as well as also product components that do not have the desired properties or do not include the relative amounts of each product of viscosity corresponding to the demand made. In this way, step (a) is often performed under conditions that are necessary to produce a product mixture that contains an undesired excess or an inadequate amount of a product to obtain the desired amount of another product. The process of the present invention solves this problem by fractionating the product mixture produced in step (a) to separate and recover one or more fractions, which contain the components having the desired properties and separating one or more other fractions. of the product mixture for further processing in step (b) of the method of this invention. In the alternative, the complete product of step (a) can be oligomerized in step (b). The fraction or fractions selected for further processing is then subjected to oligomerization conditions in contact with an oligomerization catalyst in step (b) such that a product mixture containing at least one product having desired properties and in a desired amount that is not produced in step (a). Thus, step (b) allows the olefin feed to step (a) that is more efficiently converted to desired amounts of products having desired properties. In this way, the method of the present invention allows to improve the control of the composition of the feed and allows a wide range of oil products of specific oligomer of the user to be produced. Any suitable oligomerization catalyst known in the art, especially an acidic oligomerization catalyst system, and especially Friedel-Crafts type catalysts such as acid halides (Lewis acid) or proton acid catalysts (Bronsted acid) can be employed. as the oligomerization catalyst of step (b). Examples of such oligomerization catalysts include but are not limited to BF3, BC13, BBr3, sulfuric acid, anhydrous HF, phosphoric acid, polyphosphoric acid, perchloric acid, fluorosulfuric acid and aromatic sulfuric acids, and the like. Such catalysts can be used in combination and with promoters such as water, alcohols, hydrogen halide, alkyl halides and the like. A preferred catalyst system for the oligomerization process of step (b) is the catalytic system of the BF3 promoter. Suitable promoters are polar compounds and preferably alcohols containing from about 1 to about 10 carbon atoms such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, n-hexanol, n-octanol and the like. Other suitable promoters include, for example, water, phosphoric acid, fatty acids (eg, valeric acid), aldehydes, acid anhydrides, ketones, organic esters, ethers, polyhydric alcohols, phenols, ether alcohols, and the like. Ethers, esters, acid anhydrides, ketones and aldehydes provide good promoting properties when combined with other promoters having an active proton eg water or alcohols. Promoter amounts are used that are effective to provide good conversions in a reasonable amount of time. In general, amounts of 0.01 weight percent or greater may be used, based on the total amounts of olefin reagents. Amounts greater than 1.0 percent by weight may be used but are not usually necessary. The preferred amounts vary from about 0.025 to 0.5 weight percent of the total amount of olefin reagents. Amounts of BF3 are used to provide molar ratios of BF3 to the promoter from about 0.1 to 10: 1 and preferably greater than about 1: 1. For example, amounts of BF3 are employed from about 0.1 to 3.0 weight percent of the total amount of olefin reagents. The amount of catalyst used can be kept to a minimum by bubbling BF3 into a stirred mixture of the olefin reagent only until an "observable" condition is satisfied, ie an increase of 2 ° -4 ° C in temperature. Because vinylidene olefins are more reactive than vinyl olefin, less BF3 catalyst is needed compared to the vinyl olefin oligomerization process normally used to produce PAO's. The high degree of vinylidene type unsaturation of the product of step (a) is used when the catalysts of Formula 2, 3 or 4 make the product very reactive in the oligomerization of step (b). In addition, since any complete amount of product of step (a) or one or more preselected fractions thereof can be oligomerized in step (b), it is possible in the method of this invention for the adaptation of the feed material in step (b) to produce the desired relative amounts of each product of desired viscosity without producing an excess of a product to obtain the desired amount of another desired product. A further embodiment of the method of this invention is to co-oligomerize in step (b) a pre-selected fraction of the product from step (a) with at least one vinyl olefin containing from 4 to 20 carbon atoms. This allows for the conversion of a fraction of the product from stage (a) that can not be useful, for example, the fraction of dimer, to a higher fraction, for example, a fraction of trimer, which is useful. The addition of a different vinyl olefin that is used in step (a) to the feed of step (b) allows another control of the composition of the feed to step (b), and an even wider range of oils of the user's specific oligomer to be produced. It also allows for the production of an oligomer fraction that could not easily be made from another medium, for example, co-oligomerizing the C20 polymer of step (a) with C ?2 vinyl olefin in step (b) to form mainly a C32 product. The identity of the vinyl olefin used and the relative amounts of vinyl olefin and the aforementioned fraction of the product mixture of step (a) in step (b) can be varied to control the amount of products formed in stage (b). Vinyl olefins suitable for use as additional compounds that are added to the feed for step (b) in the process contain from 4 to about 30 carbon atoms, and, preferably from 6 to 20 carbon atoms, including mixtures of the same. Non-limiting examples include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Pure vinyl olefins or a mixture of vinyl olefins and vinylidene and / or internal olefins can be used. Usually, the feed contains at least about 85 weight percent vinyl olefin. Additionally, step (b) may be run so that only a fraction of the vinyl olefin reacts with the pre-selected polymer fraction of step (a).

By varying the choice of the product fraction of step (a) which is used in the feed for stage (b) and of the added vinyl olefin in step (b), products of oligomer-specific oil can be produced. user. For example, the viscosity of such a product can be varied by changing the amount and type of vinyl olefin added to the reaction mixture for the second stage. A range of molar ratios of the aforementioned preselected fraction of the product from step (a) to the added vinyl olefin may be varied, but usually at least a molar equivalent amount of vinyl olefin is used to the pre-selected fraction before mentioned the product of step (a) to consume the aforementioned pre-selected fraction of the product of step (a). The product oils have viscosities from about 1 to 20 cSt at 100 ° C. Preferably, molar ratios of from about 10: 1 to 1: 1.5 and typically more than about 1.3: 1 of the vinyl olefin added to the aforementioned pre-selected fraction of the product of step (a) are used. feed for stage (b). The vinyl olefin is typically added at a time when at least about 30 percent by weight of the aforementioned pre-selected fraction of the product of step (a) has been oligomerized in step (b). Step (b) can be carried out at atmospheric pressure. Moderately high pressures, for example at 50 pounds per square inch, can be used and may be desirable to minimize the reaction time but are not necessary due to the high reactivity of the vinylidene olefin. The reaction times and temperatures in step (b) are chosen to efficiently obtain good conversions for the desired product. In general, temperatures from about 0 ° to 70 ° C are used with total reaction times from about 1/2 to 5 hours. The products of step (b) of the method of the present invention have the desired preselected properties, especially viscosity. Typically, the products of step (b) are characterized, followed by removal of unreacted monomer and dimer, having a viscosity between 3 and 100 cSt, a viscosity index between 110 and 180, a runoff temperature of less than -30. ° C, and volatility of Noack at 250 ° C between 2% and 25%.

The following examples serve to illustrate certain specific embodiments of the invention described herein. These examples are for illustrative purposes only and should not be construed as limiting the scope of the novel invention described herein as there are many modifications and alternative variations that will be apparent to those skilled in the art and fall within the scope and spirit of the invention. described invention.

EXAMPLES All manipulations with metallocenes and other organometallic compounds are carried out in a glovebox under nitrogen. The determination of the amount of terminal vinylidene in a fluid sample is made using NMR by integrating the peak area into the olefinic regions. Molecular weights were determined using gel permeation chromatography (CPG). All viscometric properties are measured using appropriate ASTM methods. The first three examples illustrate the polymerizations in step (a) of 1-decene catalyzed by zirconocene dichloride with a methylaluminoxane activator at three different temperatures. Example 4 differs in that it is used in place of zirconocene dimethyl with a borate activator in step (a).

EXAMPLE 1 A Parr reactor of 2 liters was charged under nitrogen with 1096 g of dry 1-decene and was taken at 65 ° C with stirring. The catalyst was prepared by pre-mixing for 10 minutes a solution of 37.0 g of bis (cyclopentadienyl) zirconium dichloride in 20 ml of toluene with 38.9 ml of a solution of methylaluminoxane (MAO) in toluene (10% by weight in toluene, d = 0.860 g / ml, 5.08% by weight of Al). The catalytic solution was injected into the Parr reactor using an injection vessel. The reaction was stirred at temperature (65 ° C) for 3 hours and then rapidly cooled by pouring the contents into a rapid-quench vessel containing 200 ml of 2N NaOH and the organic layer was washed. The organic layer was subsequently washed with distilled water (2 x 200 ml) and dried over MgSO4. The removal of unreacted decene under reduced pressure resulted in the isolation of 948.5 g of a clear fluid. Further distillation of this fluid under reduced pressure resulted in the isolation of 294.1 g (31.0%) of the dimeric C20 fluid having more than 80% vinylidene by NMR. Once the dimer was removed, the bottom fraction was hydrogenated under a standard set of hydrogenation conditions (at 170 ° C, 400 psi hydrogen, using Ni in the Kieselguhr catalyst) to produce a synthetic base material of High viscosity index (VI) that has the following properties: EXAMPLE 2 This experiment was conducted in an identical manner to Example 1 with the exception of the polymerization temperature which is at 75 ° C. After rapidly cooling and washing, removal of the unreacted decene under reduced pressure resulted in the isolation of 941.8 g of a clear fluid. Further distillation of this fluid under reduced pressure resulted in the isolation of 369.4 g (39.2%) of the dimeric C20 fluid having more than 80% vinylidene by NMR. Once the dimer was removed, the bottom fraction was hydrogenated under a set of standard hydrogenation conditions (at 170 ° C, 400 psi of hydrogen, using Ni in the Kieselguhr catalyst) to produce a synthetic base material of High viscosity index (VI) that has the following properties: EXAMPLE 3 This experiment was conducted in an identical manner to Example 1 with the exception of the polymerization temperature which is at 100 ° C. After rapidly cooling and washing, removal of the unreacted decene under reduced pressure resulted in the isolation of 908.6 g of a clear fluid. Further distillation of this fluid under reduced pressure resulted in the isolation of 475.8 g (52.4%) of the dimeric C20 fluid having more than 80% vinylidene by NMR. Once the dimer was removed, the bottom fraction was hydrogenated under a standard set of hydrogenation conditions (at 170 ° C, 400 psi hydrogen, using Ni in the Kieselguhr catalyst) to produce a synthetic base material of High viscosity index (VI) that has the following properties: EXAMPLE 4 A 2 liter Parr reactor was charged under nitrogen with 882 g of dry 1-decene and heated to 100 ° C with stirring. The catalyst was prepared by pre-mixing for 10 minutes a solution of 3.5 mg of bis (cyclopentadienyl) zirconium dimethyl in 20 ml of toluene with 11.1 mg of a solution of tetra (perfluorophenyl) borate of N, N-dimethylanalinium in 50 ml of toluene and 0.20 ml of triisobutylaluminum. The catalytic solution was injected into the Parr reactor using an injection vessel. The reaction was stirred at temperature (100 ° C) for 3 hours and then cooled rapidly by pouring the contents into a quench vessel containing 200 ml of 2N NaOH and the organic layer was washed. The organic layer was subsequently washed with distilled water (2 x 200 ml) and dried over MgSO4. The removal of unreacted decene under reduced pressure resulted in the isolation of 197.2 g of a clear fluid. Further distillation of this fluid under reduced pressure resulted in the isolation of 49.2 g (24.9%) of the dimeric C20 fluid having approximately 60% vinylidene by NMR. Once the dimer was removed, the fraction of the lower part was hydrogen under a set of standard hydrogenation conditions (at 170 ° C, 400 psi of hydrogen, using Ni in the Kieselguhr catalyst) to produce a high viscosity index (VI) synthetic base material that has the following properties: The following table shows the% C20 (decene dimer) isolated from Examples 1-4, the NMR analysis indicates more than 80% vinylidene olefin for Examples 1-3, Example 4 shows a content of About 60% vinylidene olefin: In Example 5, the dimer fraction (C20) of the product from step (a) in Examples 1-3 is reacted with 1-decene in step (b) to form a more useful product, mainly trimer (C30) ) and tetramer (C40). Example 6 demonstrates that the product of step (b) is not affected if the dimer fraction of the product of step (a) is made using a borate activator or an MAO activator.

EXAMPLE 5 A 1 liter Parr reactor was charged with 643.0 g of the C20 dimeric fluid isolated from Examples 1-3, 357.0 g of 1-decene, 2.0 g of 1-butanol and taken at 50 ° C with stirring. Boron trifluoride was introduced and adjusted slowly to a steady state pressure of 20 psi. The reaction mixture was stirred for 90 minutes. The reaction mixture was quenched with 500 g of 8% NaOH and washed with distilled water. The removal of unreacted and volatile fluids under reduced pressure (200 ° C, 0.05 mmHg) resulted in the isolation of 804.7 g of a clear fluid that was hydrogen under a set of standard hydrogenation conditions (at 170 ° C, 400 psi of hydrogen, using Ni in the Kieselguhr catalyst) to produce a base material Synthetic High Viscosity Index '(VI) that has the following properties: EXAMPLE 6 A 1 gallon Parr reactor was charged with 536.0 g of the C20 dimeric fluid isolated from runs identical to Example 4 (metallocene / borate catalyst system), 356.0 g of 1-decene, 1.0 g of 1-propanol and was taken at 35 ° C with shaking. Boron trifluoride was introduced and adjusted slowly to a steady state pressure of 20 psi. The reaction mixture was stirred for 2 hours. The product was isolated in a form identical to Example 5 which resulted in the isolation of 700.9 g of a clear fluid prior to hydrogenation. The gas chromatography analysis of this product mixture was virtually identical to the isolated product when the C20 dimeric fluid from this experiment was replaced with C20 fluid from Example 1-3. These indicated fluids having the same physical properties are obtained by dimeric products derived from the metallocene / MAO catalyst system (Examples 1-3) and the metallocene / borate catalyst system (Example 4). Example 7 illustrates the reaction of the dimer fraction (C20) of the product of step (a) with 1-dodecene to make a product of step (b), mainly C32, which could not be easily made in a high yield per any process of a stage. Example 9 differs from Example 7 because tetradecene is used in step (b), again to make a product, mainly C34, which also could not be easily made in high performance in any one-step process. Example 8 illustrates the polymerization of 1-decene in step (a) followed by the removal of an unreacted 1-decene, and the subsequent reaction of all of the remaining product from step (a) with 1-dodecene in the step (b) In this way, the dimer portion of the product of step (a) can be converted to more higher oligomers useful in step (b) with or without first removing it from the remainder of the product of step (a).

EXAMPLE 7 A 1 liter Parr reactor was charged with 651.2 g of the C20 dimeric fluid isolated from Examples 1-3, 400.1 g of 1-dodecene, 1.0 g of 1-propanol and taken at 45 ° C with stirring. Boron trifluoride was introduced and adjusted slowly to a steady state pressure of 20 psi. The reaction mixture was stirred for 2 hours. The reaction mixture was quenched with 500 g of 8% NaOH and washed with distilled water. The removal of unreacted and volatile fluids under reduced pressure (230 ° C, 0.05 mmHg) resulted in the isolation of 870.2 g of a clear fluid that was hydrogen under a standard set of hydrogenation conditions (at 170 ° C, 400 psi hydrogen, using Ni in the Kieselguhr catalyst) to produce a high viscosity index synthetic base material (VI) that has the following properties: EXAMPLE 8 Initially, a 2 liter Parr reactor was charged under nitrogen with 1094 g of dry 1-decene and taken at 100 ° C with stirring. The catalyst was prepared by pre-mixing for 10 minutes a solution of 37.0 g of bis (cyclopentadienyl) zirconium dichloride in 20 ml of toluene with 38.9 ml of a solution of methylaluminoxane (MAO) in toluene (10 wt.% In toluene; = 0.860 g / ml, 5.08% by weight of Al). The catalytic solution was injected into the Parr reactor using an injection vessel. The reaction was stirred at temperature (100 ° C) for 3 hours and then cooled rapidly by pouring the contents into a quench vessel containing 200 ml of 2N NaOH and the organic layer was washed. The organic layer was subsequently washed with distilled water (2 x 200 ml) and dried over MgSO4. The removal of unreacted decene under reduced pressure resulted in the isolation of 908.6 g of a clear fluid. In a subsequent step, a 1-gallon Parr reactor was charged with 710.0 g of previously isolated fluid, 357.0 g of 1-dodecene, 3.0 g of 1-butanol and was taken at 50 ° C with stirring. Boron trifluoride was introduced and slowly adjusted to a steady state pressure of 20 psi. The reaction mixture was stirred for 2 hours. The reaction mixture was quenched with 500 g of 8% NaOH and washed with distilled water. The removal of unreacted and volatile fluids under reduced pressure (220 ° C), 0.05 mmHg) resulted in the isolation of 844.2 g of a clear fluid that was hydrogen under a set of standard hydrogenation conditions (at 170 ° C, 400 psi of hydrogen, using Ni in the Kieselguhr catalyst) to produce a base material Synthetic High Viscosity Index (VI) that has the following properties: EXAMPLE 9 A 1 liter Parr reactor was charged with 650.0 g of the C20 dimeric fluid isolated from Examples 1-3, 350.0 g of 1-tetradecene, 1.0 g of 1-propanol and taken at 40 ° C with stirring. Boron trifluoride was introduced and adjusted slowly to a steady state pressure of 20 psi. The reaction mixture was stirred for 2 hours. The reaction mixture was quenched with 500 g of 8% NaOH and washed with distilled water. The removal of unreacted and volatile fluids under reduced pressure (248 ° C, 0.05 mmHg) resulted in the isolation of 846.7 g of a clear fluid that was hydrogen under a standard set of hydrogenation conditions (at 170 ° C, 400 psi). of hydrogen, using Ni in the Kieselguhr catalyst) to produce a high viscosity index (VI) synthetic base material having the following properties: EXAMPLE 10 An example of typical polymerization employing a catalyst selected from formulas 5-12 was made as follows: A solution of 100 mg (0.068 mmol) of Pd-a-diimine complex [2.6- (? ) 2C6H3N = C (Me) -C (Me) = NC6H32, 6 - (P r) 2Pd (CH2) 3C (O) OMe] B. { 3, 5- C6H3 (CF3) 2} 4 in 150 ml of chlorobenzene to a Parr reactor of 2 liters under nitrogen. The reactor was heated to 65 ° C and the solution was stirred by a mechanical stirrer at this temperature. The reactor was pressurized with ethylene at 100 kPa and the polymerization was continued for 10 hours. The ethylene reaction was depressurized by venting and the reaction was rapidly cooled after 10 hours in a manner similar to Example 1 and the product was isolated. It is possible to produce the product which varies in viscosity from 2 to more than 500 cSt by changing the catalyst, polymerization, temperature, ethylene pressure or a combination thereof.

EXAMPLE 11 Another typical polymerization example employing a catalyst selected from formulas 5-12 was made as follows: A solution of 100 mg was transferred (0.069 mmoles) of Pd-a-diimine complex [2,6- (, Pr) 2C6H3N = C (H) -C (H) = NC6H32, 6- (? Pr) 2Pd (CH2) 3C (0) OMe ] B. { 3,5-C6H3 (CF3) 2} 4 in 150 ml of chlorobenzene to a Parr reactor of 2 liters under nitrogen. The reactor was heated to 65 ° C and the solution was stirred by a mechanical stirrer at this temperature. The reactor was pressurized with ethylene at 100 kPa and the polymerization was continued for 10 hours. The ethylene reaction was depressurized by venting and the reaction was rapidly cooled after 10 hours in a manner similar to Example 1 and the product was isolated. It is possible to produce the product which varies in viscosity from 2 to more than 500 cSt by changing the catalyst, polymerization, temperature, ethylene pressure or a combination thereof.

EXAMPLE 12 Another example of typical polymerization employing a catalyst selected from formulas 5-12 was made as follows: A 100 mg solution was transferred. (0.068 mmol) of Pd-a-diimine complex [2,6- (? Pr) 2C6H3N = C (Me) -C (Me) = NC6H32, 6- ('Pr) 2Pd (Me) (OEt2)] B . { 3,5-C6H3 (CF3) 2} in 150 ml of chlorobenzene to a Parr reactor of 2 liters under nitrogen. The reactor was heated to 65 ° C and the solution was stirred by a mechanical stirrer at this temperature. The reactor was pressurized with ethylene at 100 kPa and the polymerization was continued for 10 hours. The ethylene reaction was depressurized by venting and the reaction was rapidly cooled after 10 hours in a manner similar to Example 1 and the product was isolated. It is possible to produce the product which varies in viscosity from 2 to more than 500 cSt by changing the catalyst, polymerization, temperature, ethylene pressure or a combination thereof.

EXAMPLE 13 Another typical polymerization example employing a catalyst selected from formulas 5-12 was made as follows: A 100 mg solution was transferred. (0.071 mmol) of Ni-a-diimine complex [2,6- (? Pr) 2C6H3N = C (Me) -C (Me) = NC6H32, 6- (? Pr) 2Ni (Me) (OEt2)] B { 3, 5- C6H3 (CF3) 2} 4 in 150 ml of chlorobenzene to a Parr reactor of 2 liters under nitrogen. The reactor was heated to 65 ° C and the solution was stirred by a mechanical stirrer at this temperature. The reactor was pressurized with ethylene at 100 kPa and the polymerization was continued for 10 hours. The ethylene reaction was depressurized by venting and the reaction was rapidly cooled after 10 hours in a manner similar to Example 1 and the product was isolated. It is possible to produce the product which varies in viscosity from 2 to more than 500 cSt by changing the catalyst, polymerization, temperature, ethylene pressure or a combination thereof.

EXAMPLE 14 Another typical polymerization example employing a catalyst selected from formulas 5-12 was made as follows: A solution of 100 mg (0.072 mmol) of Ni-a-diimine complex [2.6- (? ) 2C6H3N = C (H) -C (H) = NC6H32, 6- (Pr) 2Ni (Me) (OEt2)] B. { 3, 5- C6H3 (CF3) 2} in 150 ml of chlorobenzene to a Parr reactor of 2 liters under nitrogen. The reactor was heated to 65 ° C and the solution was stirred by a mechanical stirrer at this temperature. The reactor was pressurized with ethylene at 100 kPa and the polymerization was continued for 10 hours. The ethylene reaction was depressurized by venting and the reaction was rapidly cooled after 10 hours in a manner similar to Example 1 and the product was isolated. It is possible to produce the product which varies in viscosity from 2 to more than 500 cSt by changing the catalyst, polymerization, temperature, ethylene pressure or a combination thereof. From the above description, it is apparent that the objects of the present invention have been achieved. While only certain modalities have been established, alternative embodiments and various modifications will be apparent from the foregoing description for those skilled in the art. These and other alternatives are considered equivalent and are within the spirit and scope of the present invention. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (26)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A process for the selective production of an oligomer oil having predetermined properties, characterized in that it comprises: (a) polymerizing a feed comprising one or more C3 to C20 olefins having at least one hydrogen on the 2 carbon atoms, minus two hydrogens on the 3 carbon atoms and at least one hydrogen on the 4 carbon atoms (if at least 4 carbon atoms are present in the olefin), in the presence of a catalyst system comprising a transition metal complex of voluminous ligand of the stoichiometric Formula 1 and an activating amount of an activator comprising an organoaluminum compound or a hydrocarbylboro compound or a mixture thereof: Formula 1 LmMXnX wherein L is the bulky ligand, M is the transition metal, X and X1 may be the same or different and are independently selected from the group consisting of halogen, hydrocarbyl group or hydrocarboxyl group having 1-20 carbon atoms, where m is 1-3, n is 0-3, p is 0-3 and the sum of the integers m + n + p corresponds to the valence of the transition metal, to thereby form a product mixture comprising a product distribution of at least one fraction having properties that are outside of a predetermined classification thereof, and (b) oligomerizing at least one preselected fraction of the product mixture formed in step (a) in the presence of a catalyst of acid oligomerization to thereby form the aforementioned oligomer oil.

2. The process according to claim 1, characterized in that the aforementioned metal complex contains a multiplicity of linked atoms that form a group that can be cyclic with one or more optional heteroatoms.

3. The process according to claim 2, characterized in that the aforementioned bulky ligand transition metal complex is a metallocene, wherein the feed comprises one or more linear C3 to C20 1-olefins, and wherein the product mixture formed comprises a poly (1-olefin) or copoly (1-olefin) containing essentially 1-olefin, viscous, essentially in terminal unsaturated form of molecular weight between 300 and 10,000 having a terminal vinylidene content of more than 50%.

. The process according to claim 3, characterized in that the aforementioned poly (1-olefin) or copoly (1-olefin) has a terminal vinylidene content of more than 80%.

5. The process according to claim 3, characterized in that the metallocene is represented by the stoichiometric Formula 2 Formula 2 (Cp MR ^ R2 wherein each Cp is a substituted or unsubstituted cyclopentadienyl or indenyl ring, and each substituent may next be the same or different and is an alkyl, alkenyl, aryl, alkaryl or aralkyl radical having from 1 to 20 carbon atoms or at least two carbon atoms formed together to form a part of a C4 or C ring, wherein M is a transition metal of group IV, V or VI, wherein R1 and R2 are independently selected from group consisting of halogen, hydrocarbyl, hydrocarboxyl, each having 1-20 carbon atoms, and wherein m is 1-3, n is 0-3, p is 0-3, and the sum of m + n + p corresponds to the oxidation state of M.

6. The process according to claim 3, characterized in that the metallocene is represented by Formulas 3 or 4 Formula 3 (C5RJg) R s (C5R c MQ 3-k- Formula 4 R &C " M " wherein each C5R g is a substituted or unsubstituted cyclopentadienyl, and each R3 may be the same or different and is hydrogen, alkyl, alkenyl, alkaryl, aryl or aralkyl having from 1 to 20 carbon atoms or at least 2 carbon atoms joined together to form a part of a C4 to C6 ring; wherein R4 is either 1) an alkylene radical containing 1 to 4 carbon atoms, or 2) a dialkylgermanium radical 0 of silica or a radical of alkyl phosphoric or of amine, and R4 is a substituent on and bridge of two rings CsR3g or bridge of a ring of C5R3g subsequent to M, wherein each Q may be the same or different and is an alkyl radical, alkenyl, aryl, alkaryl or arylalkyl having 1 to 20 carbon atoms or halogen, and Q 'is an alkylidene radical having 1 to 20 carbon atoms; when k is 0, x is 1, otherwise x is always 0; and where s is 0 or 1; and when s is 0, g is 5 and k is 0, 1 or 2; and when s is 1, g is 4 and k is 1.

7. The process according to claim 5, characterized in that the metal in the aforementioned metal in the complex is a Group IVB Periodic metal.

8. The process according to claim 2, characterized in that the aforementioned bulky ligand transition metal complex has a stoichiometric formula of Formula 5 Formula 6 Formula 7 Formula 8 wherein M is selected from the group consisting of Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni, or Pd; X and X1 are independently selected from the group consisting of halogen, hydrocarbyl group and hydrocarboxyl group having from 1 to 20 carbon atoms; n and p are integers whose sum is the valence of M minus 2; R5 and R8 are each independently hydrocarbyl or substituted hydrocarbyl, with the proviso that the carbon atom attached to the imino nitrogen atom has at least two carbon atoms attached thereto; R6 and R7 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R6 and R7 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring; R3 and R, 112 'are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R 10 R 11 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R15 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl, or two of R15 taken together form a ring; R 16 is hydrocarbyl or substituted hydrocarbyl, R 13 is hydrogen, hydrocarbyl substituted hydrocarbyl or R, 16 and R taken together form a ring; R17 is hydrocarbyl or substituted hydrocarbyl, , 14 and RJ is hydrogen, hydrocarbyl substituted hydrocarbyl, or R and R taken together form a ring; each R18 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R 19 R 22 are each independently hydrocarbyl or substituted -hydrocarbyl, with the proviso that the carbon atom attached to the imino nitrogen atom has at least two carbon atoms attached thereto; R 20 and R 21 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R23 is independently hydrocarbyl or substituted hydrocarbyl with the proviso that any olefinic bond in the olefin is separated from any other olefinic or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; n in Formula 7 is 2 or 3; and with the proviso that: when the complex has the structure of the stoichiometric Formula 7, M is not Pd; and when M is Pd, no diene is present.

9. The process according to claim 8, characterized in that the transition metal is Co, Fe, Ni, or Pd.

• 10. The process according to claim 8, characterized in that the transition metal is Ni or Pd.

11. The process according to claim 8, characterized in that the complex has the structure of Formula 8.

12. The process according to claim 2, characterized in that the bulky ligand transition metal complex is a complex of the stoichiometric Formula 9: Formula 9 wherein three nitrogen atoms N1, N2 and N3 are co-ordinated to the transition metal M selected from Co, Fe, Ru and Mn; wherein G comprises one or more organic portions to which the three nitrogen atoms are collectively or separately attached N1, N2 and N3; wherein X and X1 are independently selected from the group consisting of halogen, hydrocarbyl group and hydrocarboxyl group having 1 to 20 carbon atoms; where n and p are integers whose sum is the valence of M minus 3; and where . M is Co, when the sum of the integers n and p is 1, 2, or 3, when M is Ru, the sum of n and p is 2, 3 or 4, when M is Fe, the sum of n and p is 2 or 3, and when M is Mn, the sum of n and p is 1, 2, 3 or 4.

13. The process according to claim 12, characterized in that the aforementioned metal complex has the structure of Formula 10: Formula 10 wherein M is Fe [II], Fe [III], Co [I], Co [II], Co [III], Ru [II], Ru [IV], Mn [I], Mn [II], Mn [III] or Mn [IV]; wherein X and X1 are independently selected from the group consisting of halogen, hydrocarbyl group and hydrocarboxyl group having from 1 to 20 carbon atoms; where n and p are integers whose sum is the valence of M; R24, R25, R26, R27 and R29 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and wherein (1) when M is Fe, Co or Ru, R28 and R30 are independently selected from hydrogen , halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and when any two or more of R24-R30 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, the two or more may be linked to form one or more cyclic substituents, or (2) when M is Fe, Co, Mn or Ru, then R28 is represented by the stoichiometric Formula 11, and R30 is represented by the stoichiometric Formula 12 as follows: Formula 11 Formula 12 wherein R31 to R40 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; where any of two or more of R 24 R .2"7 ', y and y- to R, 4 * 0u are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, the two or more may be linked to form one or more cyclic substituents, with the proviso that at least one of R31, R32, R33 and R34 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when none of the ring systems of Formulas 11 or 12 are part of a polyaromatic fused ring system, or (3) when M is Fe, Co, Mn Ru, then R 28 is a group having the formula -NR41R42 and R30 is a group having the formula -NR43R44, wherein R41 to R44 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or heterohydrocarbyl substituted, wherein when any two or more of R to R, R and R41 to R44 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, two or more may be attached to forming one or more cyclic substituents.

14. The process according to claim 1, characterized in that the polymerization catalyst in step (a) is a Philips chromium oxide catalyst.

15. The process according to claim 1, characterized in that the activator is aluminoxane.

16. The process according to claim 15, characterized in that the activator is selected from the group consisting of linear methylaluminoxane, cyclic methylaluminoxane and mixtures thereof.

17. The process according to claim 1, characterized in that the activator is employed at a molar ratio of from about 1 to about 5,000 moles of activator per mole of transition metal complex.

18. The process according to claim 17, characterized in that the activator is used at a molar ratio of at least about 150 moles of activator per mole of transition metal complex.

19. The process according to claim 1, characterized in that the catalyst in step (b) is a catalytic system of acid oligomerization.

20. The process according to claim 19, characterized in that the oligomerization catalyst system comprises boron trifluoride and a promoter.

21. The process according to claim 1, characterized in that the total product of step (a) is oligomerized in step (b).

22. The process according to claim 1, characterized in that a mixture of the aforementioned pre-selected fraction of the product mixture of step (a) and one or more vinyl olefins containing from 4 to 20 carbon atoms is oligomerized in the stage (b).

23. The process according to claim 22, characterized in that 1-decene is polymerized in step (a), and a mixture of the fraction of the product mixture of step (a) containing 20 carbon atoms and less and a or more linear α-olefins mentioned above are oligomerized in step (b).

24. The process according to claim 23, characterized in that the aforementioned linear alpha olefin in the mixture is 1-decene, and an oligomer oil containing 30 to 40 carbon atoms comprises at least 60% of the product of step (b) .

25. The process according to claim 23, characterized in that the aforementioned vinyl olefin in the mixture is 1-dodecene, and an oligomer oil containing 32 to 40 carbon atoms comprises at least 60% of the product of step (b) ).

26. The process according to claim 23, characterized in that the aforementioned vinyl olefin in the mixture is 1-tetradecene, and an oligomer oil containing 34 to 40 carbon atoms comprises at least 60% of the product of step (b) ).