The way to obtain oligomeric oils

 

(57) Abstract:

Study: petrochemical industry. Essence: conduct the polymerization raw material containing one or more 1-olefins from C3to C20in the presence of a catalyst comprising a catalyst of transition metal and the bulk of the ligand and then conduct the oligomerization of at least a pre-selected fraction of the obtained product, which has properties that go beyond a pre-defined interval the desired properties. Technical result: improving the quality of the target product. 25 C.p. f-crystals, 9 PL.

The level of technology

The scope of the invention

The present invention generally relates to a multistage process for the preparation of oligomeric oils and, in particular, to a multi-stage method, in which the first stage consists in the polymerization of a raw material containing one or more 1-olefins from C3to C20in the presence of a catalyst comprising a complex of a transition metal with bulky ligand, and the next stage is the oligomerization of at least a pre-selected fraction of the product obtained in the first stage.

The level of technology

Previously OPI is publ. June 23, 1994 under the number WO 94/13715, described catalytic system containing a transition metal compound with bulky ligand with the formula, which corresponds to a large extent formulas 1, 2, or 3, or 4 below. Catalytic system also includes an activator containing metal II or group III of the Periodic table of elements, in particular compounds trialkylamine, alumoxane, both linear and cyclic, or ionizing ionic activators or compounds such as tri(n-butyl) ammonium Tetra(pentafluorophenyl)boron. The described process involves the copolymerization of ethylene and alpha-olefin. Suitable alpha-olefins have one hydrogen atom at the second carbon atom, at least two hydrogen atoms at the third carbon atom or at least one hydrogen atom at the fourth carbon atom. The resulting copolymers have a high degree of content atenololatenolol or vinylidene unsaturation at the end, have an average molecular weight of from 300 to 15,000 and a molecular weight distribution (Mw/Mn) is usually less than five.

Bagheri and others in the US 5688887 disclose another process for the polymerization of a raw material containing one or more 1-olefins from C3to C20Johnson and others, PCT/US 96/01282, published. August 1, 1996 under number WO 96/23010, open processes, which use a catalytic system containing various transition metal compounds with bulky ligand, which have the formula that corresponds to a large extent formulas 5, 6, 7 or 8 below. Disclosed processes include the use of the above catalyst for polymerization of ethylene, acyclic olefins, and/or selected cilice is to obtain a wide range of homopolymers and copolymers.

In addition, there are a number of patent publications that disclose catalytic systems containing transition metal compounds with bulky ligands having the stoichiometric formula, which is similar to formula 9 or 10 below, and an activating amount of an activator chosen from organoaluminium and hydrocarbonic compounds. For example, Brikovsek, etc, PCT/GB 98/038, published. March 18, 1999 under the number WO 99/12981, reveals a catalytic system for use in the polymerization of 1-olefins. Brookhart, etc, PCT/US 98/00316, published. July 16, 1998 under number WO 98/30612, reveal a similar catalytic system for the polymerization of propylene. Brookhart and others, PCT/US 98/14306, published. January 21, 1999 under the number WO 99/02472, reveal the process of obtaining alpha-olefins by reacting ethylene in the presence of a similar catalyst system and reveal that the alpha-olefins can be further subjected homopolymerization or copolymerization with other olefins to form polyolefins or can be converted into alcohols. Bennett, PCT/US 97/23556, published. June 25, 1998 under number WO 98/27124, discloses the polymerization of ethylene in the presence of analogization polymerization of olefin monomer in the presence of a similar catalyst system, containing the compound of the transition metal with bulky ligand immobilized on the substrate material. Matsunaga and others, PCT/US 97/10419, published. December 24, 1997 under number WO 97/48737, reveal the process of homopolymerization or copolymerization of ethylene in the presence of such catalyst system at high pressure ethylene.

The greatest problem encountered in the production of oligomeric oils from vinyl olefins, is what is normally a mixture of oligomeric products should be subjected to fractionation to obtain separate fractions, to obtain oil with a given desired viscosity (e.g., 2, 4, 6, or 8 cSt at 100C). As a result, the commercial production is difficult to obtain the mixture of oligomeric products, from which, after fractionation get the appropriate quantity of each product with its viscosity, in accordance with the requirements of the market, so it is often necessary to produce an excess of one of the products to get the required amount of the other. Another problem is the lack of control of chemical process and the isomerization of alpha-olefins to internal olefins. The third problem is that the processes of the polymer is as a lubricant too volatile). Thus, it is necessary to develop a process that provides multilateral able to find the viscosity of the product with high selectivity and produce the target oil pre-selected desired viscosity easily and with high reproducibility.

Schaerfl and other, US 5284988 and 5498815 reveal two two-stage process of synthetic oils that do provide multilateral able to find the viscosity synthetic oils with high selectivity. US 5284988 discloses a process which provides increased selectivity in the formation of synthetic oils derived from olefins, vinylidene olefins and alpha-olefins. The process for US 5284988 related to the production of synthetic oil, includes (a) the isomerization of at least a part of raw materials from vinylidene olefins in the presence of isomerization catalyst with formation of an intermediate product, which contains tizamidine olefin and (b) codimerization intermediate product with at least one vinyl olefin in the presence of the oligomerization catalyst with the formation of synthetic oil, which contains stimer vinylidenes of olefin and vinyl olefin. the by known methods, such as dimerization of vinyl olefins containing from 4 to about 30 carbon atoms, preferably at least 6 and most preferably at least 8 to about 20 carbon atoms, including mixtures thereof. Suitable vinyl olefins, which can be used at the stage of codimerization process US 5284988, contain from 4 to about 30 carbon atoms and preferably from about 6 to about 24 carbon atoms, including mixtures thereof. At the stage of codimerization may be used any suitable catalyst for the dimerization, known from the prior art, and in particular the catalysts for Friedel-such as acid halides (Lewis Acid or a proton acid (Acid Bronsted), which can be used in combination with promoters.

US 5498815 discloses a process for the production of synthetic oil, which includes stages of interaction vinylidenes of olefin in the presence of a catalyst with the formation of the intermediate mixture, which contains at least about 50 weight percent dimer vinylidenes of the olefin, and then adding to the resulting intermediate mixture of vinyl olefin and their interaction in the presence of a catalyst so that the formed cylindrowym the olefin. Suitable for the first stage of this process vinylidene olefins can be obtained using known methods, such as dimerization of vinyl olefins containing from 4 to about 30 carbon atoms. Suitable for use in the second stage of this process vinyl olefins containing from 4 to about 30 carbon atoms. At both stages may be used any suitable catalyst for the dimerization, known from the prior art, and in particular the catalyst type catalysts for Friedel-such as galogenangidridy acid (Lewis Acid or a proton acid (Acid Bronsted), and the catalysts can be used in combination with each other.

Hobbs and others, PCT/US 90/00863, published. 7 September 1990 under number WO 90/10050, disclose a method of improving thermal stability of synthetic lubricating oils derived from oligomers of alpha-olefins, by alkylation in the presence of an acid alkylation catalyst such olefin, as a mission, or a low molecular weight olefins, do not belong to the series of greases obtained in the oligomerization of 1-alkenes. Oligomers of alpha-olefins obtained by oligomerization of raw materials consisting of from a6to C20alpha oledenenie of the mixture of oligomers, containing olefinic hydrocarbons range of lubricants.

However, neither of US 5284988, neither of US 5498815, no PCT/US 90/00863 do not disclose a multi-stage process comprising a first stage of polymerization of the olefin in the presence of a catalytic system containing a complex of the transition metal and the bulk of the ligand with formation of the final mixture, including the distribution of the products, at least one of the fractions which has properties beyond their predefined range, and the subsequent stage of oligomerization of at least a pre-selected fraction of the mixture of products formed in the first stage.

Objectives of the invention

Thus the present invention is the provision of an improved process of obtaining oligomeric oils that have predefined properties, which allow to solve the above problems, known from the prior art.

In particular, the present invention is the provision of the above-mentioned improved process, which allows for a greater degree of control over the chemistry of the process and reduce the degree of isomerization of the double bond of olefinic materials.

An additional objective of the present invention is lenovich oligomeric olefins in the oil, yousee predefined properties.

Other objectives and advantages will become apparent as the familiarization with the following detailed description and claims.

The essence of the invention.

These tasks are solved by the process of the present invention, which consists in the selective production of oligomeric oils that have predefined properties, and includes a first stage (a) polymerization of a raw material containing one or more from C3to C20olefins having at least one hydrogen atom on the 2nd carbon atom, at least two hydrogen atoms on the 3rd carbon atom and at least one hydrogen atom on the 4th carbon atom (if at least 4 carbon atom present in the olefin), in the presence of a catalytic system containing a complex of the transition metal and the bulk of the ligand of formula 1 and an activating quantity of an activator containing organoaluminium or hydrocarbone compound or a mixture of:

Formula 1

LmMXnX"p.

In formula 1, L is a bulky ligand, M represents a transition metal, X and X ' may be the same or different and independently selected from groups who, has a value of 0-3, R has a value of 0-3, and the sum of the integers m+n+p corresponds to the valency of the transition metal. This forms a kind of mixture of products that contains a set of products, at least a fraction of which has such properties that go beyond their predefined properties. At a subsequent stage (b) conduct the oligomerization of at least a pre-selected fraction of the mixture of product from step (a) in the presence of acid catalyst in the oligomerization, thus formed the aforementioned oligomeric oil

Detailed description of preferred embodiments of the invention

The catalytic system used in stage (a) of the method according to the invention, includes a complex of the transition metal and the bulk of the ligand stoichiometric formula 1

Formula 1

LmMXnX"p,

where L is a bulky ligand, M represents a transition metal, X and X ' may be the same or different and independently selected from the group comprising halogen, hydrocarbon or hydrocarbons containing 1-20 carbon atoms, and where m has a value of 1-3, n has a value of 0-3, R has a value of 0-3, and the sum of the integers m+n+p according to the MOU, forming a group that may be cyclic group, optionally containing one or more heteroatoms. The ligands L and X can be related to each other, and, if there are two ligands L and/or X, they can form a bridge.

In one of preferred embodiments of the invention the catalyst is metallocen, M represents a transition metal of the IV, V or VI group and one or more L represents cyclopentadienyls or intenally balance. In this embodiment of the invention, the feedstock contains one or more linear from C3to C201-olefins and a mixture of products formed in stage (a) contains mainly unsaturated at the end of a viscous, mostly 1-registergui poly(1-olefin) or copoly(1-olefin) of molecular weight in the range of from 300 to 10,000, in which the content end vinylidene is more than 50%, preferably more than 80%. Preferably metallocene represented by the stoichiometric formula 2:

Formula 2

(Cp)mMR1nR2p,

where each CP is a substituted or unsubstituted cyclopentadienyls or indanilnykh ring, with each Deputy may be the same or they are different, and is about 20 carbon atoms or at least two carbon atoms, together with the education part of the ring that contains4or C6; where R1and R2independently selected from the group consisting of halogen, hydrocarbon or hydrocarbons, each of which contains from 1 to 20 carbon atoms; where m has a value of 1-3, n has a value of 0-3, R has a value of 0-3, and the sum of m+n+p corresponds to the oxidation state of M

In alternative preferred embodiments of the invention metallocene represented by the stoichiometric formula 3 or 4

Formula 3

Formula 4

where each5R3gis a substituted or unsubstituted cyclopentadienyl, each R3may be the same or different and represents hydrogen, alkyl, alkenyl, alkaryl or aralkyl containing from 1 to 20 carbon atoms or at least two carbon atoms joined together with formation of the rings, containing from C4to C6; R4is either 1) alkalinity radical containing from 1 to 4 carbon atoms, or 2) dialkylamino, or silicon, or alkylphosphonyl or amine radical and R4Deputy and connects two of the C5R3gring or attaches one number is th, alkanniny, aryl, alkalline or arylalkyl radical containing from 1 to 20 carbon atoms or halogen, Q' is alkylidene radical containing from 1 to 20 carbon atoms; and 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 set to 5 and k is 0, 1 or 2; and when s is 1, g is set to 4 and k is set to 1. M represents a transition metal of the IV, V or VI, preferably the IV group.

In another preferred embodiment of the invention the catalyst instead of metallocene is a complex stoichiometric formulas 5, 6, 7 or 8, containing bidentate ligand:

Formula 5

Formula 6

Formula 7

Formula 8

In formulas 5-8 transition metal M is chosen from the group consisting of Ti, Zr, Sc, V, Cr, rare earth metal, Fe, Co, Ni or Pd; X and X1independently selected from the group consisting of halogen, hydrocarbonous or hydrocarbonbearing group containing from 1 to 20 carbon atoms; n and p are integers whose sum represents the valence of M minus 2 (the number of links between M and bidentate ligand); R5the m carbon linked to the nitrogen atom of aminogroup, has at least two carbon atoms associated with it; R6and R7each independently represents hydrogen, hydrocarbon, substituted hydrocarbon, or R6and R7taken together, represent hydrocarbide or substituted hydrocarbide, forming a carbocyclic ring; R9and R12each independently represents hydrogen, hydrocarbon or substituted hydrocarbon; R10and R11each independently represents hydrogen, hydrocarbon or substituted hydrocarbon; each R15is independently hydrogen, hydrocarbon or substituted hydrocarbon, or two R15taken together form a ring; R16represents hydrocarbon or substituted hydrocarbon, and R13represents hydrogen, hydrocarbon or substituted hydrocarbon or R16and R13taken together form a ring; R17represents hydrocarbon or substituted hydrocarbon, and R14represents hydrogen, hydrocarbon or substituted hydrocarbon, or R17and R14taken together form a ring; each R18represents independently hydrogen, hydrocarbon or substituted hikoki, that the carbon atom bound to the nitrogen atom of aminogroup, has at least two associated carbon atoms; R20and R21are independently hydrogen, hydrocarbon or substituted hydrocarbon; each R23represents independently hydrocarbon or substituted hydrocarbon, provided that any olefinic bond in the specified olefin is separated from the other olefinic communication or aromatic ring Quaternary carbon atom or at least two saturated carbon atoms. When M is a Pd a diene is not present, and when using a complex formula 7, M is Pd. M preferably represents Co, Fe, Ni or Pd, more preferably Ni or Pd. In the formula 7 n represents 2 or 3.

In another preferred embodiment of the invention, instead of metallocene or complex, including bidentate ligand specified complex of the transition metal and the bulk of the ligand is a complex stoichiometric formula 9

Formula 9

where three carbon atoms, N1N2and N3coordinating associated with a transition metal M selected from Co, Fe, Ru and mn; where G contains one or more organic residues to the IMO selected from the group containing halogen, hydrocarbonous group and hydrocarbonbearing group containing from 1 to 20 carbon atoms; n and p are integers, the sum of which represents the valency of M minus 3 (the number of links between M and tridentate ligand); and when M represents Co, the sum of n and p is 1, 2, or 3, when M represents Ru, the sum of n and p is 2, 3 or 4, when M represents Fe, the sum of n and p is 2 or 3, and when M is an MP, the sum of n and p is 1, 2, 3 or 4. In the most preferred embodiment of the complex of formula 9 above complex of the metal has the structural formula 10:

Formula 10

where M represents Fe[II], Fe[III], Co[I], Co[II], Co[III], Ru [II], Ru[IV], Mn[I], Mn[II], Mn[III] or Mn[IV]; where X and X1independently selected from the group consisting of halogen, hydrocarbonous group and hydrocarbonbearing group containing from 1 to 20 carbon atoms; where n and p are integers whose sum represents the valency of M; R24, R25, R26, R27and R29independently selected from hydrogen, halogen, hydrocarbide, substituted hydrocarbide, heterodidaskalia or substituted heterodidaskalia, and

(1) when M represents Fe, Co interoperatable or substituted heterodidaskalia; and when any two or more 24- R30are hydrocarbon, substituted hydrocarbon, heteroeroticism or substituted heteroeroticism, the two or more groups may be linked to form one or more cyclic substituents, or

(2) when M represents Fe, Co, Mn or Ru, then R28represented by the stoichiometric formula 11 and R30represented by the stoichiometric formula 12:

where R31-R40independently selected from hydrogen, halogen, hydrocarbide, substituted hydrocarbide, heterodidaskalia or substituted heterodidaskalia; and when any two or more24-R27, R29and R31-R40are hydrocarbon, substituted hydrocarbon, heteroeroticism or substituted heteroeroticism, the two or more groups may be linked to form one or more cyclic substituents; with the proviso that at least one of R31, R32, R33and R34represents hydrocarbon, substituted hydrocarbon, heterogeneous or substituted heterogeneous, when neither of the ring systems of formulae 11 and 12 is not part of polyaromatic kondensirovannoi the battle group, contains the formula-NR41R42and R30represents a group of formula-NR43R44where R41-R44independently selected from hydrogen, halogen, hydrocarbide, substituted hydrocarbide, heterodidaskalia or substituted heterodidaskalia; and when any two or more groups R24-R27, R29and R41-R44are hydrocarbon, substituted hydrocarbon, heterogeneous or substituted heterogeneous, such two or more groups may be linked to form one or more cyclic substituents.

In addition to the complex of the transition metal and the bulk of the ligand, the catalytic system used in stage (a) of the method according to the invention, contains an activating quantity of an activator selected from alyuminiiorganicheskikh connections, as well as hydrocarbonic connections.

Suitable alyuminiiorganicheskikh compounds include compounds of the formula AlR503where each R50independently represents a C1-C12alkyl or halogen. Examples include trimethylaluminum (TMA), triethylaluminium (TEA), triisobutylaluminum (TIBA), tri-n-octylamine, methylaluminoxane, ethylaluminum dichloride, dimey. Alumoxane well known from the prior art as typical oligomeric compounds that can be obtained by controlled addition of water to alkylamino connection, for example, trimethylaluminum. Such compounds can be linear, cyclic or mixtures thereof. Commercially available alumoxane usually are mixtures of linear and cyclic compounds. Cyclic alumoxane can be represented by the formula [R51AlO]sand linear alumoxane the formula R52(R53AlO)swhere s denotes a number from about 2 to 50, and where R51, R52and R53are gidrolabilna group, preferably1-C6alkyl groups, e.g. methyl, ethyl or butylene group. Alkylalkoxy, such as methylalumoxane (MAO), preferred.

Particularly preferred mixtures alkylalkoxy and trialkylaluminium compounds, such as MAO with TMA or TIBA. In this context it should be noted that the term "alkylalkoxy" as it is used, means in this description of commercially available alkylalkoxy that may contain a portion, usually about 10 weight percent, but not necessarily to 50 mass% matched with rimacillin (TMA), while commercial MMO contains both TMA and TIBA. The number alkylalkoxy mentioned here include impurities trialkylamine, and accordingly it is assumed that the number trialkylaluminium compounds mentioned herein include the compounds of formula lR3in addition to any AIR3the compound included in the composition alkylalkoxy, when it is present.

Examples of suitable hydrocarbonic compounds include braccini, trimethylboron, criativo, dimethylphenylacetate(phenyl) borate, titillate(phenyl)borate, triphenylboron, Tetra(pentafluorophenyl)borate of dimethylphenylamine, tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate of sodium, titillate(pentafluorophenyl)borate and Tris(pentafluorophenyl)boron.

In the manufacture of the catalyst according to the present invention, the amount of activating compound selected from alyuminiiorganicheskikh and hydrocarbonic compounds that should be used is easily determined with a simple test, for example, by making a small test samples, which can be used for polymerization of small amounts of monomer(s) and determining the activity of the obtained catalyst. As the government is occhialino from 1 to 2000 atoms of aluminium or boron per atom of transition metal in the compound of formula 1. As a rule, use about 1 mole to about 5000 moles, preferably up to about 150 moles of activator per mole of the complex transition metal.

When the catalytic system used in stage (a) of the method according to the invention, contains complex formulas 5-12, the catalyst preferably contains a neutral Lewis base, in addition to the complex volume of the ligand with the transition metal and the activator. Neutral base Lewis is well known from the technical field related to technology polymerization catalyst of the Ziegler-Natta. Examples of classes of neutral Lewis bases suitable for use in the present invention include unsaturated hydrocarbons such as alkenes (other than 1-olefins or alkynes, primary, secondary and tertiary amines, amides, phosphoramides, phosphines, phosphites, ethers, thioethers, nitrites, carbonyl compounds, for example, esters, ketones, aldehydes, carbon monoxide and carbon dioxide, sulfoxidov, sulfones and braccini. Despite the fact that 1-olefins capable of acting as a neutral Lewis bases, for the purposes of the present invention, they are considered to be monomers or comonomers 1-olefins, and non-neutral grounds Lietojamam the invention are considered to be neutral Lewis bases. Preferred Lewis bases are tertiary amines and aromatic esters, for example, dimethylaniline, diethylaniline, tributylamine, ethylbenzoic and benzyl benzoate. In this particular embodiment of the present invention the complex of the transition metal (first component), the activator (the second component) and a neutral Lewis base (the third component) of the catalytic system can be introduced simultaneously or in any desired sequence. However, if the above-mentioned second and third component are compounds that interact strongly with each other, for example, form a stable compound, is preferred simultaneous introduction of either of the above first and second components, or above the first and third components at the initial stage before the introduction of the last of specific components. Preferably, if the first and third components are in contact with each other before introducing the second component. Suitable are the quantities used to prepare the catalytic system of the first and second components, which are defined above with respect to the catalysts of the present invention. The number of neutral base Lewis (components is that from 100:1 to 1:1000, most preferably in the range from 10:1 to 1:20. All three component catalytic system can be put together, for example, as a pure material, in suspension or in the form of a solution of the material in a suitable diluent or solvent (for example, liquid hydrocarbon), or if at least one of the components is volatile, by using the vapor of this component. Components can be put together at any desired temperature. The components are mixed with each other at room temperature, as a rule, is satisfactory. Heated to high temperatures, for example up to 120°C, if desired, can be carried out, for example, to achieve a better mixing of the components. It is preferable to carry out the simultaneous introduction of all three components in an inert atmosphere (e.g., dry nitrogen) or vacuum. Optionally, you can apply the catalyst to the substrate (see below), this can be accomplished, for example, by first creating a catalytic system containing three components, and, preferably, impregnation of the substrate to its solution, or by introducing into the substrate to one or more components simultaneously or sequentially. Optionally, the substrate itself p sevkazenergo third component. Examples of the substrate material having the properties of a neutral base Lewis are poly(aminosterol) or a copolymer of styrene and aminosterol (i.e vinylsilane).

The catalysts of the present invention can optionally contain more than one of the above defined compounds of the transition metal. The catalyst may contain, for example, a mixture of complexes of 2,6-diacetylpyridine(2,6-diisopropylphenyl)FeCl2and 2,6-diacetylpyridine(2,4,6-trimethylene)Fl2or a mixture of 2,6-diacetylpyridine(2,6-diisopropylphenyl)Col2and 2,6-diacetylpyridine(2,4,6-trimethylene)Fl2. In addition to the specified one or more specific compounds of the transition metal 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 this type, which is used in conventional catalyst systems of the Ziegler-Natta catalysts based on metallocenes or activated by heating chromocene catalysts on a substrate (for example, catalyst type Philips).

The catalyst used in process stage (a) of the present invention, can be established,and LCD. Suitable substrate of the solid particles usually contain a polymer or a refractory oxide materials, with each of them is preferably porous, such as, for example, talc, inorganic oxides, inorganic chlorides, for example magnesium chloride, and polymer substrate materials, such as polystyrene, polyolefin, or other polymeric compounds or any other organic substrate materials and the like, which preferably have an average particle size greater than 10 microns. Preferred substrate materials are inorganic oxides that include oxides of metals and metalloids, which are elements 2, 3, 4, 5, 13 or 14 groups of the Periodic table. In the preferred embodiment of the invention, the substrate materials for the catalyst include silicon oxide, aluminum oxide, aluminum silicate and a mixture thereof. Other inorganic oxides that may be used, alone or in combination with silicon oxide, aluminum oxide or aluminum silicate, are magnesium oxide, titanium, zirconium and the like.

Preferably, the substrate material had a surface area in the range of from about 10 to about 700 m2/g, the pore volume was in the interval is doctitle surface area ranges from about 50 to about 500 m2/g, pore volume is in the range from about 0.5 to about 3.5 cm3/g and average particle size is in the range from about 20 to about 200 microns. Most preferably the surface area is in the range from about 100 to about 4002/g; pore volume is in the range from about 0.8 to about 3.0 cm3/g and average particle size from about 30 to about 100 microns. The pore size of the carrier according to the invention is usually in the range from 10 to about 1000 Å, preferably 50 to about 500, and more preferably 75 to about 350 F. the Compound of the transition metal with bulky ligand is applied to the substrate material in the form of a layer, usually at the level of the load from 100 to 10 micromol compounds of transition metal per gram of the solid substrate; more preferably from 80 to 20 micromol compounds of transition metal per gram of the solid substrate, and most preferably from 60 to 40 micromol compounds of transition metal per gram of the solid substrate. Since the compound of the transition metal with bulky ligand may be applied as a layer on a substrate to any level up to the pore volume of the substrate, the utilization levels less than 100 micromol compounds of transition metal per gram of the substrate are prefer is the Eney than 60 micromol compounds of transition metal per gram of the solid substrate the most preferred.

Impregnation of the substrate material can be carried out using conventional methods, for example, by obtaining a solution or suspension of the catalyst components in a suitable diluent or solvent or suspension together with the substrate material. The substrate material impregnated catalyst may then be separated from the diluent, for example, by filtration or evaporation. If desired, the catalysts may be formed in situ in the presence of the substrate material or the substrate material may be pre-impregnated or pre-mixed simultaneously or sequentially with one or more components of the catalyst. The formation of the catalyst on the substrate can be carried out, for example, by treatment of the transition metal compounds according to the present invention alumoxane in a suitable inert diluent, for example, volatile hydrocarbon, the suspension of the particles of the substrate material with the product and evaporation of the volatile diluent. The resulting catalyst on the substrate is preferably in the form of easily flowing powder. The number of the used substrate material can vary widely, for example, from 100,000 to 1 gram per gram of metheney maybe for example, is performed in the liquid phase, slurry phase or gas phase periodically, continuously, or semi-continuous, at the temperature of polymerization in the range from -100 to +300°C. In the case of carrying out the process in the phase of the suspension or in the gas phase, the catalyst is generally introduced into the polymerization zone in the form of solid particles. This solid catalyst may be, for example, undiluted solid catalytic system formed from the complex of the transition metal and the bulk of the ligand used in the method according to the present invention, and activator, or may be a solid complex. In the latter case, the activator can be introduced into the polymerization zone, for example, in the form of a solution, separately or together with the solid complex.

In the polymerization process in the phase suspension of solid particles of a catalyst or a catalyst on a substrate introduced into the polymerization zone or in the form of a dry powder or in suspension in the diluent phase polymerization. Preferably the particles are introduced into the polymerization zone in the form of a suspension in the diluent phase polymerization. Area polymerization can be, for example, an autoclave or similar reaction vessel, or continuous con is sa.

Ways of implementation of the gas-phase polymerization process is well known from the prior art. Such methods typically include mixing (e.g., shaking, vibration or fluidization) of the catalyst layer or the layer of the target polymer (i.e. polymer, which has the same or similar properties that are desirable to achieve in the polymerization process), containing the catalyst, and the introduction of flow of monomer are at least partially in the gaseous phase under conditions in which at least part of the monomer is polymerized in contact with a layer of catalyst. The catalyst layer typically cooled using cold gas (e.g., recirculating gazoobraznogo monomer) and/or volatile liquid (e.g., volatile inert hydrocarbon or gaseous monomer, which was condensed with the formation fluid). Formed and isolated from the gas-phase process, the polymer is formed directly in the form of solids in the polymerization zone, and he is free from liquid or substantially free from liquid. As is well-known specialist in this field if any liquid be allowed to fall into the zone of gas-phase polymerization process, the amount of butyrate with "liquid-phase" processes, in which the resulting polymer is dissolved in a solvent, and processes in the suspension phase, in which the polymer is formed in the form of a suspension in a liquid diluent.

Stage (a) of the present invention can be carried out in a periodic, semi-continuous or in the so-called "continuous" conditions using methods well known in the prior art. The process of polymerization in stage (a) of the method according to the present invention is preferably carried out at a temperature above 0 C, particularly preferably above 15C. Maintaining the polymerization process in these certain temperature intervals can be useful from the point of view of controlling the average molecular weight of the polymeric product.

Monomers which are suitable for use as the olefin, which is subjected to the reaction in stage (a) of the process according to the present invention are alpha-olefins, which have (1) at least one hydrogen atom at the second carbon atom, (2) at least two hydrogen atoms at the third carbon atom, and (3) at least one hydrogen atom at the 4 carbon atom (if at least 4 carbon atom present in the olefin). Thus, suitable alpha-olefin my or branched alkyl radical, containing from 1 to 18 carbon atoms, and where any branching, which is present, is one or more atoms that are not nearer the double bond than 4 carbon atoms. R60represents an alkyl, preferably containing from 1 to 19 carbon atoms and more preferably from 2 to 13 atoms. Thus, useful alpha-olefins include propylene, 1-butene, 1-penten, 4-methyl-1-penten, 1-hexene, 1-hepten, 1-octene, 1-none, 1-mission 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecane, 1-hexadecene, 1-heptadecene, 1 octadecene, 1-nonadecane and mixtures thereof.

Stage (a) of the process according to the present invention is controlled so as to obtain a polymer having an average number molecular weight of not more than 15,000, and is usually from 300 to 15,000, and preferably from 400 to 8000. Brednikova molecular weight for such polymer can be determined by any known suitable methods. One way to determine is pressure chromatography (also known as helpanimals chromatography, GPC), which also gives information on the molecular mass distribution (see W. W. Yau, J. J. Kirkland and D. D. BIy, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979). Molecular mass is sustained fashion less than 4, more preferably less than 3, for example, it is between 1.5 and 2.5.

When using a catalyst of the formula 2, 3 or 4, the polymer obtained in stage (a) according to the invention is additionally characterized by the fact that they have up to about 50% or more of polymer chains with terminal unsaturation acylanilides type. A small number of polymer chains can contain terminal vinyl unsaturation, which is a POLY-CH=CH2and part of the polymers can contain internal monoisocyanates, for example, POLY-(T')=(SN(T2), where T1and T2each independently represents an alkyl group containing from 1 to 18, preferably up to 8 carbon atoms, and POLY represents the polymer chain. The products of the polymerization stage (a) according to the invention contain circuits that can be saturated by hydrogen, but preferably contain a polymer chain at least 50, preferably at least 60, and more preferably at least 75% (e.g 75-98%) which contain end atenololatenolol (vinylidene) unsaturation. The percentage of polymer chains containing atenololatenolol unsaturation may be determined by using Spectro occhialini embodiments of the invention, stage a) is carried out in liquid-phase conditions using a catalytic system, containing a catalyst of the formula 2, 3 or 4, in which M represents a transition metal of group IVb, usually titanium, zirconium or hafnium, and alumoxane as activator in a molar ratio of alumoxane to metallocene 150 or more, and C3-C20alpha-olefins in the composition of the raw material containing more than 1 mass% of at least one volatile hydrocarbon liquid, but consisting mainly of C3-C20alpha-olefins, polimerizuet with the formation of mainly unsaturated at the end, viscous, mostly 1-registergui poly(1-olefins) or copoly(1-olefin) having a content of terminal vinylidene more than 50%.

In this preferred embodiment of the invention unsaturated at the end, viscous polymeric product according to the invention is essentially poly(1-olefin) or copoly(1-olefin). Polymer chain viscous polymers obtained in stage (a) of the method according to the invention are mainly unsaturated at the end. Under the expression "mainly unsaturated at the end" is meant that preferably more than about 90% of the polymer chains contain unsaturation, more preferably more than about 95% of the polymer chains in the polymer product contains not end the bretania, additionally characterized owing to the removal of light components (<s), a viscosity of between 5 and 200 cSt, a viscosity index between 110 and 230, a pour point of less than - 20C and volatility in the Place (Noack) when S between 1 and 20%.

When using the catalyst of the formula 9, 10, 11 or 12, the polymer obtained in stage (a) according to the invention is also characterized, due to the removal of light components (<s), viscosity between 5 and 230 cSt, a viscosity index between 110 and 200, a pour point of less than - 20C and volatility over the Place when S between 1 and 20%.

In General, the products obtained in stage (a) are mixtures in which the components and their relative amounts depend solely on the alpha-olefin reactant used catalyst and the process conditions. Usually the products are unsaturated and have a viscosity lying in the range of from about 2 to about 100 cSt at 100C. At least a portion of a mixture product, as a rule, has desirable properties, such as viscosity, for a particular application. Components in this part of the products is usually hydronaut to improve their resistance to oxidation, and they have a long safety, low volatility, low point pour point and high viscosity indices of technology in this field.

However, usually, this product mix includes a significant amount of unreacted olefinic feedstock, as well as the components, which have no necessary properties or do not include the relative amount of each viscous product that meets the requirements of the market. So, stage (a) is often carried out in conditions that are required to obtain a mixture of products that contain unwanted excess or inadequate quantity of one product in order to obtain the desired quantity of another product.

The process of the present invention solves this problem by fractionation of the mixture of products obtained in stage (a) in order to separate and to isolate one or more fractions containing components having desirable properties, and separating one or more other fractions of the mixture of products for additional process stage (b) of the method according to the invention. Alternative entire product of stage (a) may be subjected to oligomerization stage (b).

Faction(s) selected for further process, then subjected to the action of oligomerization conditions in contact with an oligomerization catalyst in stage (b) so that the mixture productory not formed in stage (a). Thus, the stage (b) allows to convert the olefinic feedstock from step (a) with the greatest efficiency in the desired number of products having desirable properties. Thus, the method according to the present invention allows better control over the conversion of raw materials and allows to obtain a wide range of required specific oligomeric oils.

Any suitable catalyst for oligomerization, known from the prior art, in particular an acid catalytic system oligomerization and in particular catalysts of the type of Friedel-such as acid halides (Lewis Acid or a proton acid (Acid Bronsted), can be used as a catalyst for the oligomerization stage (b). Examples of such oligomerization catalysts include, without limitation, F3, BCl3, VVG3, sulfuric acid, dry HF, phosphoric acid, polyphosphoric acid, perchloro acid, persulfates, aromatic sulfonic acids and the like. Such catalysts can be used in combination and together with promoters, such as water, alcohols, hydrogen halides), alkylhalogenide and the like. The preferred catalytic system stage (b) is occhialino alcohols, containing from about 1 to 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, aldehydes, fatty acids (for example, valerianic acid), acid anhydrides, ketones, organic esters, ethers, polyhydrogenated alcohols, phenols, ethers, alcohols and the like. Ethers and esters, anhydrides, acids, ketones and aldehydes provide the best properties of promoters, when they are combined with other promoters having active hydrogen, such as water or alcohols.

The number of promoters that are used, are effective to ensure a more complete transformation within a reasonable time. As a rule, can be used in amounts of 0.01 mass% or more, calculated on the total amount of reactive olefins. Quantities exceeding 1.0 mass percent, can also be applied, but this is usually not required. Preferred amounts are in the range from about 0.025 to 0.5 to weight percent calculated on the total number of reactive olefins. Use the same quantities F3to ensure sportsouth number F3from about 0.1 to 3.0 mass% per the total amount of olefin reactants.

The amount of catalyst used can be maintained at a minimum by ozonation F3stir in a mixture of olefinic reagent only as long until you met "observed" condition, i.e., the temperature increase of 2-4°C. Because vinylidene olefins are more reactive than vinyl olefins, requires less catalyst F3compared to the oligomerization of vinyl olefins, typically used for the production of radioactive waste.

High unsaturation vinylidene type of product of stage (a), when using the catalysts of formulas 2, 3, or 4, makes the product very reactive at the stage of oligomerization (b). In addition, since either the entire quantity of the product of stage (a), or one or more pre-selected fractions can be subjected oligomerization at the stage (b) is possible in the method according to the invention to select raw materials for stage (b) to produce the desired relative amounts of the desired products, with its viscosity, without obtaining the excess of one of the products that the invention is cooligomerization at the stage (b) pre-selected fraction of the product of stage (a) at least one vinyl olefin, containing from 4 to 20 carbon atoms. This leads to the transformation of the fraction of the product of stage (a), which may not be desired, for example, dimeric fraction, the higher the fraction, for example, in the trimeric fraction, which is useful. Adding another vinyl olefin than that used in stage (a), to the raw material stage (b) allows additional control over the transformation of the raw materials stage (b) and even increase the range of the ordered specific oligomeric oils that need to be done. It also allows you to get a fraction of oligomers, which cannot easily be obtained in other ways, for example, cooligomerization20polymer from stage (a) with C12vinyl olefin in stage (b) with the formation of predominantly32product. The identity used vinyl olefin and the relative amounts of vinyl olefin and the above-mentioned fraction of the mixture of the products of stage (a) at the stage (b) can be changed in order to control the amount formed in stage (b) products.

Vinyl olefins suitable for use as a complementary connection that should be added to the raw material stage (b) in this process contain from 4 to about 30 atoms plegan, 1-penten, 1-hexene, 1-hepten, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 akoten and the like. Can be used pure vinyl olefins or a mixture of vinyl and vinylidene and/or internal olefins. Usually the raw material contains at least about 85 weight percent vinyl olefins. Advanced stage (b) may be such that only a fraction of the vinyl olefin reacts with the pre-selected fraction of the polymer phase (a).

By varying the choice of the fraction of the product of stage (a) which is sent as raw material in stage (b), and vinyl olefin added in stage (b) can be obtained predetermined specific oligomeric oils. For example, the viscosity of the product can be varied by changing the number and type of vinyl olefin added to the reaction mixture in the second stage. Interval molar ratios above a pre-selected fraction of the product of stage (a) to add the vinyl may vary, but typically use at least a molar equivalent quantity of the vinyl olefin to the above-mentioned pre-selected fraction of the product of stage (a) in order to fully ispolzal 1 to 20 cSt at 100° C. Preferably the molar ratio from about 10:1 to 1:1.5, and more typically about 1.3:1 added vinyl olefin to the above-mentioned pre-selected fraction of the product of stage (a) is used as a raw material stage (b). Vinyl olefin is usually added at a time when at least about 30 mass percent above the pre-selected fraction of the product of stage (a) were subjected to oligomerization stage (b).

Stage (b) can be carried out at atmospheric pressure. Slightly elevated pressure, for example up to 50 pounds per square inch, may be used and may be desirable to reduce the response time, however, they are not necessary because vinylidene olefins are reactive compounds. The time and temperature of reaction in stage (b) is chosen in such a way as to achieve a good conversion to the desired product. Typically use a temperature from about 0 to 70C with a total reaction time of from about 1/2 to 5 hours.

The products from step (b) of the method according to the present invention have pre-selected desirable properties, particularly viscosity. Usually the products of stage (b) are characterized by, after removing the non-is 0, point pour point less than-30C and volatility over the Place when S between 2 and 25%.

The following examples are intended to illustrate specific embodiments of the invention below. These examples are only for illustrative purposes and should not be construed as limiting the scope of the new invention disclosed here, because there are many alternative modifications and options that are available to specialists in this field and which will fall within the scope and spirit of the claimed invention.

EXAMPLES

All manipulations with metallocene and other organometallics compounds is performed in closed vessels in a stream of nitrogen. The determination of the number of end vinylidene in a liquid sample carried out using NMR by integration of the peak areas in the olefinic areas. Molecular weight determined using gel chromatography (GPC). All the viscous properties were determined using the appropriate ASTM methods.

The first three examples illustrate the polymerization in stage (a) 1-mission-catalyzed dichloride of zirconocene with methylalumoxane activator at three different temperatures. Example 4 is different those eactor Parra in the current nitrogen load g 1-mission and heated to 65°C. under stirring. The catalyst is prepared by pre-mixing for 10 minute solution 37,0 mg dichloride bis(cyclopentadienyl)zirconium in 20 ml of toluene from 38.9 ml methylalumoxane (MAO) in toluene (10 wt.% in toluene, d=0,860 g/ml, 5,08 wt.% A1). The solution containing the catalyst, is introduced into a Parr reactor using an injection system. The reaction mass is stirred at a temperature of (65S) for 3 hours and then cooled rapidly by pouring the contents into a strongly cooled vessel containing 200 ml of 2N NaOH, the organic layer is separated and washed. Then the organic layer is successively washed with distilled water (I ml) and dried over MgSO4. Unreacted mission is distilled off under reduced pressure, get 948,5 g of a transparent liquid. Further distillation of this liquid under reduced pressure yields 294,1 g (31,0%) liquid dimer C20, containing according to NMR data more than 80% of vinylidene. After removal of the dimer remaining at the bottom of the fraction hydronaut standard hydrogenation conditions (at 170°C, 400 psi (2.8 MPa) hydrogen, when using Ni catalyst on kieselguhr), to obtain a high viscosity index (VI) synthetic core product having the following properties:

EXAMPLE 2

EXAMPLE 3

The experiment is carried out under the conditions of example 1 except that the polymerization is carried out at a temperature of 100C. After Sahelian and washing unreacted mission is distilled off under reduced pressure, the result is 908,6 g of a transparent liquid. Further distillation of this liquid under reduced pressure allows to obtain 475,8 g (52,4%) liquid dimer C20, containing according to NMR data more than 80% of vinylidene. After removal of the remaining dimer fraction is subjected to hydrogenation under standard hydrogenation conditions (when S, 400 psi (2.8 MPa) hydrogen, when using Ni catalyst on kieselguhr) get the OS is A 2-liter Parr reactor in a stream of nitrogen placed 882 g of dry 1-mission and heated to 100°C. with stirring. The catalyst is prepared by pre-mixing for 10 minutes a solution of 3.5 mg dimetilan(cyclopentadienyl) zirconium in 20 ml of toluene 11.1 mg of a solution of N,N-dimethylanilinium Tetra(perftoralkil) borate in 50 ml of toluene and 20 ml of triisobutylaluminum. The catalyst solution is introduced into a Parr reactor using an injection system. The reaction mixture is stirred at a temperature (100°C) for 3 hours and then quenched, pouring the contents into a strongly cooled vessel containing 200 ml of 2N NaOH, the organic layer is separated and washed. The organic layer is successively washed with distilled water (I ml) and dried over MgSO4. Removing unreacted mission under reduced pressure resulting in 197,2 g of a transparent liquid. Further distillation of this liquid under reduced pressure allows to obtain 49.2 g (24,9%) liquid dimer C20, containing according to NMR about 60% of vinylidene. After removal of the remaining dimer fraction hydronaut in conditions standard mode hydrogenation (at 170°C, 400 psi (2.8 MPa), when using Ni catalyst on kieselguhr), get the main product with high viscosity index (VI) with the following properties:

The following table shows % C20 (dimer products of examples 1-3; example 4 shows that the content vinylidenes of olefin is about 60%.

In example 5, the fraction of dimer (C20) of the product of stage (a) obtained in examples 1-3, reacts with 1-mission at the stage (b), it is more commonly used product, the native trimer (C30) and the tetramer (C40). Example 6 shows that the product of stage (b) remains unchanged if the dimeric fraction of the product of stage (a) the benefits of using borate activator or activator MAO.

EXAMPLE 5

1-galany reactor Parra download 643,0 g of liquid C20 dimer isolated from examples 1-3, 357,0 g 1-mission, 2.0 g of 1-butanol and brought to 50°C. with stirring. Add boron TRIFLUORIDE and slowly set pressure 20 psi (0,14 bar). The reaction mixture is stirred for 90 minutes, then quenched with 500 g of 8% NaOH and washed with distilled water. Remove unreacted and volatile liquids under reduced pressure (200°C, 0.05-Hg psi (2,8 bar), get in the 804,7 g of a transparent liquid, which is subjected to hydrogenation in the usual standard hydrogenation conditions (at 170°C, 400 psi (2.8 MPa) hydrogen, when using Ni catalyst on kieselguhr), get the main product with high index vasc ujaut 536,0 g of liquid C20 dimer, highlighted in the implementation process under conditions identical to example 4 (catalytic system: metallocen/Borat), 356,0 g 1-mission, 1.0 g of 1-propanol and incubated at 35C with stirring. Introducing boron TRIFLUORIDE and then slowly set pressure 20 psi (0,14 bar). The reaction mixture is stirred for 2 hours. The product is extracted according to the method similar to the method of example 5, receiving the hydrogenation 700,9 g of a transparent liquid product. Gas chromatographic analysis of the mixture of products was virtually identical to the analysis of the product selected in the case where the liquid dimer C20 in this experiment, replace the liquid C20 from examples 1-3. This means that the liquid having the same physical properties obtained for the dimeric products formed from metallocene/MAO catalytic system (examples 1-3) and metallocene/borate catalyst system (example 4).

Example 7 illustrates the reaction of the dimer fraction (C20) of the product of stage (a) with 1-dodecanol, upon receipt of the product of stage (b), mainly C32, which cannot be easily obtained with high yield using a one-stage process. Example 9 differs from example 7 that tetradecene used in stage (b), in turn the steps of any one-step process.

Example 8 illustrates the polymerization of 1-mission stage (a), followed by removal of unreacted 1-mission and subsequent reaction of the remaining products of stage (a) with 1-mission at the stage (b). Thus, dimeric part of the product of stage (a) can be transformed into a more suitable higher oligomers at the stage (b) with or without first removing them from the residual product of stage (a).

EXAMPLE 7

The Parr reactor in 1 gallon fill 651,2 g of liquid dimer C20, selected from examples 1-3, 400,1 g 1-dodecene, 1.0 g of 1-propanol, bring to 45C under stirring. Introducing boron TRIFLUORIDE and slowly bring the pressure up to 20 psi (0,14 bar). The reaction mixture is stirred for 2 hours and then quenched with 500 g of 8% NaOH and washed the distillated water. After removal of unreacted and volatile liquids under reduced pressure (230S, 0.05 mm Hg) get 870,2 g of a transparent liquid, which is subjected to hydrogenation in accordance with standard hydrogenation conditions (when S, 400 psi (2.8 MPa) hydrogen, using no catalyst on kieselguhr) with a core product with high viscosity index (VI) with the following properties:

EXAMPLE 8

First 2-liter. utilizator prepare pre-mix for 10 minute solution 37,0 mg dichloride bis(cyclopentadienyl)zirconium in 20 ml of toluene from 38.9 ml methylalumoxane (MAO) in toluene (10 wt.%, d=0,860 g/ml, 5,08 wt.% A1). The catalytic solution is injected into the reactor Parra using the injection apparatus. The reaction mixture is stirred at a temperature (100C) for 3 hours and then quenched by pouring the contents into a strongly cooled vessel containing 200 ml of 2N NaOH, the organic layer is separated and washed. The organic layer is successively washed with distilled water (2200 ml) and dried over MgSO4. Removing unreacted mission under reduced pressure allows you to select 908,6 g of a transparent liquid. At the next stage, 1-gallon Parr reactor load 710,0 g above the selected liquid, 357,0 g 1-dodecene, 3.0 g of 1-butanol and heated under stirring to 50 ° C. Introducing boron TRIFLUORIDE and then slowly bring the pressure up to 20 psi (0,14 bar). The reaction mixture is stirred for 2 hours, then quenched with 500 g of 8% NaOH and washed with distilled water. Remove unreacted and volatile liquids under reduced pressure (220C, 0,05 MND) that allows to allocate 844,2 g prozacnationmovie Ni catalyst on kieselguhr), get the main product with high viscosity index (VI) with the following properties:

EXAMPLE 9

1-gallon Parr reactor load 650,0 g of liquid C20 dimer isolated from examples 1-3, 350,0 g 1-tetradecene, 1.0 g of 1-propanol and the temperature is brought to 40 ° C under stirring. Introducing boron TRIFLUORIDE and slowly bring the pressure up to 20 psi (0,14 bar). The reaction mixture is stirred for 2 hours, quenched with 500 g of 8% NaOH and washed with distilled water. Remove unreacted and volatile liquids under reduced pressure (S, 0,05 MND), the result 846,7 g of a transparent liquid, which hydronaut using a standard set of conditions of hydrogenation (S, 400 psi (2.8 MPa) hydrogen, when using Ni catalyst on kieselguhr), get the main product with high viscosity index (VI) with the following swistami:

EXAMPLE 10

A typical example of a polymerization using a catalyst selected from formulas 5-12 presented as follows: a solution of 100 mg (0,068 mmol) Pd-a-tiaminovogo complex [2,6-(1Pr)2C6H3N=C(Me) C(Me)=NC6H32,6-(1Pr)2Pd(CH2)3C(O)OMe]B{ 3,5-C6H3(CF3)3}4in 100 ml of chlorobenzene SIP the Alcoy at the same temperature.

In the reactor pump ethylene to 100 kPa and the polymerization continued for 10 hours. The pressure of ethylene dropping through the hole, and the reaction quenched after 10 hours in a manner similar to described in example 1, the product is isolated. It is possible to obtain a product of different viscosity from 2 to more than 500 cSt as a result of replacement of the catalyst, the temperature of polymerization, the pressure of ethylene or combinations thereof.

EXAMPLE 11

Another typical example of the polymerization process using a catalyst selected from formulas 5-12 performed as follows. A solution of 100 mg (0,069 mmol) Pd-a-tiaminovogo complex [2,6-(1Pr)2C6H3N=C(H)-C(H)=NC6H32,6-(1Pr)2Pd(CH2)3C(O)OMe] {3,5-C6H3(CF3)2}4in 150 ml of chlorobenzene are placed in a 2-liter Parr reactor under a stream of nitrogen. The reactor is heated to 650°C and the solution is stirred with a mechanical stirrer at room temperature. In the reactor pump ethylene to 100 kPa and the polymerization are within 10 hours. The pressure of ethylene dropping through the hole, and the reaction is stopped after 10 hours in a manner similar to that described in example 1, and the product isolated. It is possible to obtain a product of different viscosity from 2 to 500 cSt for ASS="ptx2">Another typical example of the polymerization process uses a catalyst selected from formulas 5-12 performed as follows. A solution of 100 mg (0,068 mmol) Pd-a-tiaminovogo complex [2,6-(1Pr)2C6H3N=C(Me)=NC6H32,6-(1Pr)2Pd(Me)(OEt2)]B{3,5-(C6H3(CF3)2}4in 150 ml of chlorobenzene was placed in a Parr reactor under a stream of nitrogen. The reactor was filled with ethylene to 100 kPa and the polymerization continued for 10 hours. Relieve pressure of ethylene through the hole, and the reaction quenched for 10 hours in the usual way described in example 1, and the product is extracted. It is possible to obtain a product of different viscosity from 2 to 500 cSt by changing the catalyst, the temperature of polymerization, the pressure of ethylene or a combination of these options.

EXAMPLE 13

Another typical example of the polymerization process using a catalyst selected from formulas 5-12 performed as follows. A solution of 100 mg (0,071 mmol) Ni-a-tiaminovogo complex

[2,6-(1Pr)2C6H3N=C(Me) C(Me)=NC6H32,6-(1Pr)3Ni(Me)(OEt2)]B{3,5-C6H3(CF3)2}4in 100 ml of chlorobenzene are placed in a 2-liter Parr reactor under a stream of nitrogen. The reactor is heated is placed 100 kPa and the polymerization continued for 10 hours. Relieve pressure of ethylene through the hole, and the reaction quenched after 10 hours in the usual manner similar to that described in example 1, the product is isolated. It is possible to obtain a product of different viscosity from 2 to 500 cSt due to the replacement of the catalyst, polymerization temperature, pressure ethylene or combinations thereof.

EXAMPLE 14

Another typical example of the polymerization process, comprising a catalyst selected from formulas 5-12 performed as follows. A solution of 100 mg (0,072 mmol) Ni-a-tiaminovogo complex

[2,6-(1Pr)2C6H3N=C(H)-C(H)=NC6H32,6-(1Pr)2Ni(Me)(OEt2)]B{3,5-(C6H3(CF3)2}4in 150 ml of chlorobenzene are placed in a 2-liter Parr reactor under a stream of nitrogen. The reactor is heated to 65°C. and the solution stirred with a mechanical stirrer at this temperature. The reactor was filled with ethylene to a pressure of 100 kPa and the polymerization continued for 10 hours. The pressure of ethylene dropping through the hole, and the reaction quenched after 10 hours in the usual way as in example 1 and the product isolated. It is possible to obtain a product of different viscosity from 2 to 500 cSt as a result of replacement of the catalyst, changing the temperature of polymerization, the pressure of ethylene or combinations thereof.

1. The way to obtain oligomeric oils with predefined properties, including (a) polymerization of a raw material containing one or more olefins from C3to C20having at least one hydrogen atom at the second carbon atom, at least two hydrogen atoms at the 3rd carbon atom and at least one hydrogen atom at the 4th carbon atom, in the presence of the olefin, in the presence of a catalytic system comprising a complex of a transition metal with bulky ligand stoichiometric formula 1, an activating quantity of an activator containing alyuminiiorganicheskikh or hydrocarbone compound or their mixture

LmMXnX1p,

where L is a bulky ligand;

M represents a transition metal;

X and X1may be the same or different and independently selected from the group comprising halogen, hydrocarbon or hydrocarbons containing 1-20 carbon atoms;

m has a value of 1-3;

(b) oligomerization of at least a pre-selected specified fraction of the mixture of products formed in the first stage (a) in the presence of acid oligomerization catalyst with the formation of the target oligomeric oils.

2. The method according to p. 1, characterized in that the metal complex contains many related atoms forming a group that may be cyclic group, optionally containing one or more heteroatoms.

3. The method according to p. 2, characterized in that the complex of the transition metal with bulky ligand is metallocen, raw material contains one or more linear 1-olefins from C3to C20and the resulting mixture of products contains essentially unsaturated at the end of a viscous, mostly 1-olefin-containing poly(1-olefin) or copoly(1-olefin) of molecular weight between about 300 and about 10,000, in which the content of vinylidene at the end is more than 50%.

4. The method according to p. 3, characterized in that poly(1-olefin)or copoly(1-olefin)s content vinylidene on cichecki formula 2

(Cp)mMR1nR2p,

where each CP is a substituted or unsubstituted cyclopentadienyls or indanilnykh ring, with each Deputy may be the same or they are different and represents alkyl, alkanniny, aryl, alkalline or Uralkaliy radical containing from 1 to 20 carbon atoms, or at least two carbon atoms joined together with formation of the rings, containing from C4to C6;

M represents a transition metal of group IV, V or VI;

R1and R2independently selected from the group consisting of halogen, hydrocarbon or hydrocarbons, each of which contains from to 20 carbon atoms;

m has a value of 1-3, n has a value of 0-3, R has a value of 0-3, and the sum of m+n+p corresponds to the oxidation state of M

6. The method according to p. 3, characterized in that metallocene represented by formula 3 or 4

(C5R3g)toR4s(C5R3g)MQ3-K-x,

or

R4s(C5R3g)2MQ1,

where each C5R3gis a substituted or unsubstituted cyclopentadienyl, each R4to C6;

R4is either 1) alkalinity radical containing from 1 to 4 carbon atoms, or 2) dialkylamino or silicon or alkylphosphonyl or amine radical and R4Deputy and connects two of the C5R3gring or attaches one C5R3gring to M;

each Q may be the same or different and represent alkyl, alkanniny, aryl, alkalline or arylalkyl radical containing from 1 to 20 carbon atoms or halogen;

Q' represents alkylidene radical containing from 1 to 20 carbon atoms;

when k is 0, x is 1, otherwise x is always 0;

s is 0 or 1;

when s is 0, g is set to 5 and k is 0, 1 or 2;

and when s is 1, g is set to 4 and k is set to 1.

7. The method according to p. 5, characterized in that the metal in the metal complex is a metal of group IVB of the Periodic system.

8. The method according to p. 2, characterized in that idea

or

or

where M is chosen from the group consisting of Ti, Zr, Sc, V, CR, rare-earth metal, Fe, Co, Ni, or Pd;

X and X1independently selected from the group consisting of halogen, hydrocarbonous or hydrocarbonbearing group containing from 1 to 20 carbon atoms;

n and p are integers, the sum of which determines the valence of M minus 2;

R5and R8each independently represents hydrocarbon, or substituted hydrocarbon, provided that the carbon atom bound to the nitrogen atom imino group has at least two carbon atoms associated with it;

R6and R7each independently represents hydrogen, hydrocarbon, substituted hydrocarbon, or R6and R7taken together constitute hydrocarbide or substituted hydrocarbide, forming a carbocyclic ring;

R9and R12each independently represents hydrogen, hydrocarbon or substituted hydrocarbon;

R10and R11each independently represents hydrogen, hydrocarbon or substituted hydrocarbon;

each R15is independently hydrogen, hydrocarbon or substituted hydrocarbon, and the hydrated hydrocarbon, and R13represents hydrogen, hydrocarbon or substituted hydrocarbon or R16and R13taken together form a ring;

R17represents hydrocarbon or substituted hydrocarbon, and R14represents hydrogen, hydrocarbon or substituted hydrocarbon, or R17and R14taken together form a ring;

each R18independently represents hydrogen, hydrocarbon or substituted hydrocarbon;

R19and R22represent independently hydrocarbon or substituted hydrocarbon, provided that the carbon atom bound to the nitrogen atom imino group, has at least two associated carbon atoms;

R20and R21are independently hydrogen, hydrocarbon, or substituted hydrocarbon;

each R23represents independently hydrocarbon or substituted hydrocarbon, provided that any olefinic bond in the specified olefin is separated from the other olefinic communication or aromatic ring Quaternary carbon atom or at least two saturated carbon atoms;

n in the formula 7 represents 2 or 3;

provided that when the complex has the following class statement="ptx2">9. The method according to p. 8, wherein the transition metal is Co, Fe, Ni or Pd.

10. The method according to p. 8, wherein the transition metal is Ni or Pd.

11. The method according to p. 8, wherein the complex has the structural formula 8.

12. The method according to p. 2, characterized in that the complex of the transition metal with bulky ligand is a complex stoichiometric formula 9

where three carbon atoms, N1N2and N3coordinating associated with a transition metal M selected from Co, Fe, Ru and mn;

G contains one or more organic residues, to which three atoms of nitrogen N1N2and N3attached separately or together;

X and X1independently selected from the group consisting of halogen, hydrocarbonous group and hydrocarbonbearing group containing from 1 to 20 carbon atoms;

n and p are integers, the sum of which represents the valency of M minus 3; and when M represents Co, the sum of n and p is 1, 2, or 3, when M represents Ru, the sum of n and p is 2, 3, or 4 when M represents Fe, the sum of n and p is 2 or 3, and when M is an MP, the sum of n and p is 1, 2, 3, or 4.

X and X1independently selected from the group consisting of halogen, hydrocarbonous group and hydrocarbonbearing group containing from 1 to 20 carbon atoms;

n and p are integers whose sum represents the valency of M;

R24, R25, R26, R27and R29independently selected from hydrogen, halogen, hydrocarbide, substituted hydrocarbide, heterodidaskalia or substituted heterodidaskalia,

while (1) when M represents Fe, Co or Ru, R28and R30independently selected from hydrogen, halogen, hydrocarbide, substituted hydrocarbide, heterodidaskalia or substituted heterodidaskalia; and when any two or more 24-R30are hydrocarbon, substituted hydrocarbon, heteroeroticism or substituted heteroeroticism, the two or more groups may be linked to form one or more cyclic substituents, or (2) when M represents Fe, Co, Mn or Ru, then R28represented by the stoichiometric formula 11 and R30represented by the stoichiometric formula 12

where R31-R40independently vitroceramica; and when any two or more24-R27, R29and R31-R40are hydrocarbon, substituted hydrocarbon, heteroeroticism or substituted heteroeroticism, the two or more groups may be linked so that form one or more cyclic substituent; provided that at least one of R31, R32, R33and R34represents hydrocarbon, substituted hydrocarbon, heterogeneous or substituted heterogeneous, when neither of the ring systems of formulae 11 and 12 do not form part of the condensed polyaromatic cyclic system, or (3) when M represents Fe, Co, Mn or Ru, then R28represents a group having the formula-NR41R42and R30represents a group of formula-NR43R44where R41-R44independently selected from hydrogen, halogen, hydrocarbide, substituted hydrocarbide, heterodidaskalia or substituted heterodidaskalia; and when any two or more groups R24-R27, R29and R41-R44are hydrocarbon, substituted hydrocarbon, heterogeneous or substituted heterogeneous, such two or more groups can be tie ctivator is iluminacin.

15. The method according to p. 14, characterized in that the activator is selected from the group consisting of linear methylalumoxane, cyclic methylalumoxane and mixtures thereof.

16. The method according to p. 1, characterized in that the activator is used in a molar ratio of from about 1 to about 5000 moles of activator per mole of the complex transition metal.

17. The method according to p. 16, characterized in that the activator is used in a molar ratio of at least about 150 moles of activator per mole of the complex transition metal.

18. The method according to p. 1, characterized in that the catalyst of stage (b) is an acid catalytic system oligomerization.

19. The method according to p. 18, characterized in that the catalytic system oligomerization contains boron TRIFLUORIDE and the promoter.

20. The method according to p. 1, characterized in that the entire product of stage (a) is subjected to oligomerization stage (b).

21. The method according to p. 1, characterized in that the mixture of the specified pre-selected fraction of the product of stage (a) and one or more vinyl olefin containing from 4 to 20 carbon atoms, is subjected to oligomerization stage (b).

22. The method according to p. 21, characterized in that 1-the mission is subjected to polymerization in stage (a), and the linear alpha-olefins is subjected to oligomerization stage (b).

23. The method according to p. 22, wherein the linear alpha-olefin in the mixture is a 1-mission and oligomeric oil containing from 30 to 40 carbon atoms that includes at least 60% of the product of stage (b).

24. The method according to p. 22, characterized in that the vinyl olefin in the mixture is a 1-dodecen, and oligomeric oil containing from 32 to 40 carbon atoms that includes at least 60% of the product of stage (b).

25. The method according to p. 22, characterized in that the vinyl olefin in the mixture is a 1-tetradecene, and oligomeric oil containing from 34 to 40 carbon atoms, contains at least 60% of the product of stage (b).

 

Same patents:

The invention relates to a method for producing a catalytic composition, which is used for polymerization of at least one monomer to obtain a polymer, where the specified catalytic composition is produced by interaction of ORGANOMETALLIC compound, of at least one alumoorganic compounds and fluorinated solid oxide compound that is selected from a silicon oxide - titanium oxide or silicon oxide - oxide-zirconium, and boron compounds and alumoxane essentially no

The invention relates to the field of polymerization of olefins

The invention relates to the field of polymerization of olefins

FIELD: polymerization catalysts.

SUBSTANCE: invention describes metallocene catalytic component of catalytic system for production of polyolefin with isotactic or syndiotactic/isotactic block structure with length of monomer unit up to C10, said component having general formula R"(CpR1R2R3)(Cp'R1R2')MQ2, where Cp represents cyclopentadienyl ring substituted by at least one substituent; Cp' is substituted fluorenyl ring; R" structural bridge imparting steric rigidity; R1 optional substituent in cyclopentadienyl ring located at a distance to bridge and including a bulky group XR*3 wherein X is selected from group IVA elements and R*, the same or different, are hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms; R2 optional substituent in cyclopentadienyl ring, nearest to bridge and not vicinal to remote substituent, which substituent has formula YR# wherein Y is selected from group IVA elements and R#, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R3 optional substituent in cyclopentadienyl ring, nearest to bridge and being hydrogen or having formula ZR$ wherein Z is selected from group IVA elements and Rs, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R1' and R2' are independent substituents in fluorenyl ring, one of them having formula AR3’’’ wherein A is selected from group IVA elements and each of R’’’ represents independently hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms and the other being hydrogen or second group AR3’’’; M is transition metal from group IVB or vanadium and each Q is either hydrocarbon radical with 1-20 carbon atoms or halogen.

EFFECT: enabled preparation isotactic or syndiotactic/isotactic block polymer with length of monomer unit up to C10.

30 cl, 13 dwg, 2 tbl, 10 ex

FIELD: metalloorganic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to class of metallocene compounds of the general formula (I) wherein Y means fragment of the formula (II) wherein A means sulfur or selenium atom; B means carbon atom; D means carbon atom; R1, R2, R3, R4 and R5 mean hydrogen atom or hydrocarbon groups; Z is taken among fragment of the formula (II) and fragment of the formula (III) wherein R6, R7, R8 and R9 mean hydrogen atom or hydrocarbon groups; L means bivalent bridge group; M means zirconium atom; X means halogen atom; p = 2. Above described metallocenes are useful especially for polymerization of propylene.

EFFECT: improved preparing method, valuable properties of metallocenes.

15 cl, 5 tbl, 18 ex

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

FIELD: vinylcyclohexane-based polymer or copolymer with isotactic structure.

SUBSTANCE: claimed polymer or copolymer may be obtained using comonomers selected from at least one monomer of group including olefine, (meth)acrylic alkyl esters, cyclopentadiene, cyclohexene, cyclohexadiene, optionally substituted norbornene, dicyclopentadiene, optionally substituted tetracyclododecenes, alkylated in nuclear styrene, alpha-methylstyrene, divinylbenzene, vinyl ester, vinyl ether, vinyl acetate, vinyl acid, (meth)acrylonitrile, maleic anhydride. Polymer contains more than 50.1 % and less than 74 % of isotactic diads.

EFFECT: polymer of high transparency useful as material for substrate in optical memory devices.

3 cl, 4 ex, 2 tbl

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to novel organometallic compounds and to olefin polymerization catalytic systems including such organometallic compounds, and also to a method for polymerization of olefins conduct in presence of said catalytic system. Novel organometallic compound is prepared by bringing into contact (i) compound of general formula I: (I), where Ra, Rb, Rc, and Rd, identical or different, represent hydrocarbon groups; and (ii) Lewis acid of general formula MtR

13
, where Mt represents boron atom and R1, identical or different, are selected from halogen and halogenated C6-C30-aryl groups.

EFFECT: enabled preparation of novel olefin polymerization cocatalysts, which reduce use of excess cocatalyst relative to alkylalumoxanes, do not lead to undesired by-products after activation of metallocene, and form stable catalytic compositions.

14 cl, 1 tbl, 32 ex

FIELD: olefin polymerization.

SUBSTANCE: invention relates to method for introducing of several catalysts in gas-phase or suspension reactor. Claimed method includes integration before introducing into single reactor of (a) solution, suspension or emulsion containing the first catalytic substance; and (b) solution, suspension or emulsion containing the second catalytic substance and optionally activator; followed by (c) introducing of (a) and (b) composition into single reactor in presence of hydrogen and one or more olefins wherein one polyolefin composition is formed.

EFFECT: polymers with wide bimodal molecular mass distribution.

14 cl, 3 ex

FIELD: olefin polymerization.

SUBSTANCE: invention relates to method for introducing of several catalysts in gas-phase or suspension reactor. Claimed method includes integration before introducing into single reactor of (a) solution, suspension or emulsion containing the first catalytic substance; and (b) solution, suspension or emulsion containing the second catalytic substance and optionally activator; followed by (c) introducing of (a) and (b) composition into single reactor in presence of hydrogen and one or more olefins wherein one polyolefin composition is formed.

EFFECT: polymers with wide bimodal molecular mass distribution.

14 cl, 3 ex

FIELD: chemical industry; production of catalytic compounds for polymerization of monomers.

SUBSTANCE: the invention is dealt with the field of polymerization of the monomers and with the methods of production of catalytic compounds and compounds, which are applied at polymerization of at least one monomer. The offered methods contain: 1) a treated solid oxide compound produced due to a contact at least of one solid oxide with at least of one compound having an electron-seeking anion; 2)a metallocenes compound of a metal from IVA group; 3) an organoaluminum compound. The technical result: production of a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

EFFECT: the invention allows to produce a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

71 cl, 99 ex, 13 tbl

FIELD: polymers, chemical technology, catalysts.

SUBSTANCE: invention relates to the modified chrome oxide catalytic systems on a carrier used for polymerization of olefins and to a method for preparing polymers and ethylene copolymers. Invention describes a method for preparing copolymer of ethylene and 1-hexene wherein indicated copolymer shows swelling value by mass less about 380% and wherein swelling extruded flow is less about 42%, cracking resistance under external stress (ESCR) (condition A) is above about 400 h, onset of destruction of extrusion flow is at least about 2000 c-1 and result in testing for outlet for 1 min is at least about 1200 g/min in the content of xylene-soluble substances is less 0.7% and less 2 wt.-% of substance with molecular mass less 1000 Da. Method involves contact of the following components under condition of suspension polymerization in isobutene as a solvent at temperature from about 93.3°C to 110°C: (a) monomer of ethylene; (b) 1-hexene; (c) catalytic system comprising chrome applied on silicon dioxide-titanium oxide carrier that comprises from about 0.5 to about 3 wt.-% of titanium relatively to carrier mass wherein indicated catalytic system shows the surface square in the range from about 100 m2/g to about 500 m2/g, pore volume in the range from about 0.6 to about 1.4 ml/g and indicated catalytic system is activated at temperature in the range from about 538°C to about 650°C; (d) from about 0.1 to about 2.0 mg/kg relatively to a diluting agent in reactor, trialkylboron; and (e) extraction of copolymer. Also, invention describes copolymer of ethylene and 1-hexene prepared by above described method, catalytic composition and composition comprising copolymer of ethylene and 1-hexene. Invention provides enhanced yield of polymer, preparing copolymer of ethylene of high density with high resistance against cracking under stress, creating a polymer that is processed good in forming by bulge.

EFFECT: improved method for polymerization.

13 cl, 3 tbl, 1 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely XkSiCl4-k, wherein X is OR' or R', in which R can be C1-C4-alkyl or phenyl, and k=1-2. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 13 ex

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