Solid activating support for olefin polymerization catalyst

Abstract

The inventions relate to olefin polymerization processes. The invention describes: compounds that act as solid activating supports; catalysts; and catalytic compositions containing olefin polymerization catalysts that comprise said solid activating supports having the formula (I): support - O - A. In the compounds expressed by this formula, the support is a solid substrate of an inorganic oxide, and A is a polyfluorinated functional group bound to an oxygen atom on the substrate surface and having the general formula: [C(R1 ) (R2 )-O-MLn]z+ (Cty+ )z / y (II), where M is selected from the group consisting of an atom of aluminium, gallium, boron, a group 3 transition metal, and lanthanide; L is a ligand; n is 2, 3 or 4; z is 0 or 1, and Cty+ is a cation capable of converting a neutral transition metal complex into a cationic complex capable of catalyzing olefin polymerization, with a charge y, where y is 1 or 2. The invention makes it possible to use olefin polymerization catalysts on solid supports in suspension processes and gas-phase processes, thereby producing polyolefins in the form of powders having a narrow particle size distribution and a high bulk density.

Description

[0001] A solid activating support for an olefin polymerization catalyst, a method for producing it, an olefin polymerization catalyst, a method for producing it, and a catalytic composition containing it

[0002] Field of technology

[0003] The invention relates to solid activating supports for olefin polymerization catalysts, methods for their production, olefin polymerization catalysts containing said solid activating support, methods for their production, and catalytic compositions containing said catalysts.

[0004] State of the art

[0005] Immobilization of single-center olefin polymerization catalysts on solid supports allows their use in suspension and gas-phase processes, making it possible to obtain polyolefins in the form of powders with a narrow particle size distribution and high bulk density.

[0006] Single-site olefin polymerization catalysts are formed by the interaction of a precatalyst and an activator. The reaction between the neutral precatalyst complex and the activator produces a cationic complex, which is an active catalyst for olefin polymerization.

[0007] A neutral transition metal complex belonging to the classes of metallocenes, semi-metallocenes or post-metallocenes is used as a precatalyst.

[0008] Alkyl aluminoxanes, particularly methyl aluminoxane (MAO), are used as activators for single-site precatalysts. Their disadvantage is the need for a large excess of activator relative to the single-site precatalyst (MAO / precatalyst molar ratio = 100-1000 / 1). Tris(perfluoroaryl)boranes or perfluoroaryl borates (BARF) are also used to activate single-site precatalysts. They are used in stoichiometric quantities (BARF / precatalyst molar ratio ≈ 1 / 1). Their disadvantages include low thermal and chemical stability, sensitivity to solvents and trace impurities, and high cost.

[0009] A good alternative to BARF-type activators are activators based on aluminum perfluoroalcoholates, such as tris(perfluoroalcoholates) or tetrakis(perfluoroalcoholates) aluminum, which are characterized by a lower price, but at the same time form catalysts that are not inferior in activity to catalysts based on BARF-type activators.

[0010] Inorganic oxides are primarily used as solid carriers, in particular silica gel, aluminum oxide and aluminosilicates of various grades.

[0011] Immobilization of a catalyst based on BARF-type activators requires the creation of a covalent bond between the support surface and either the precatalyst or the activator. This ensures more reliable catalyst attachment to the support surface than physical sorption without covalent bonding, which can lead to partial leaching of the catalyst from the support surface, potentially leading to highly undesirable fouling of the resulting polymer on the reactor's interior.

[0012] Immobilization of the precatalyst on the support surface via a covalent bond requires the introduction of appropriate reactive groups into the structure of the precatalyst ligand, which makes the synthesis of the precatalyst more expensive.

[0013] One of the disadvantages of covalently immobilized catalysts with borate activators is the possible rupture of the boron-oxygen bond with subsequent transfer of the metallocene, semi-metallocene or post-metallocene in the form of a cation to the surface of the support with the formation of a particle inactive in polymerization.

[0014] Catalysts for the polymerization of olefins containing aluminum perfluoroalcoholates as activators, which have a number of advantages over BARF-type activators, are known only in homogeneous form (i.e., not immobilized on the surface of a solid support), which does not allow the advantages of aluminum perfluoroalcoholates as activators to be used in gas-phase and suspension processes. The essence of the invention

[0015] The inventors have discovered that treating the surface of a carrier with carbonyl compounds, which results in the attachment of surface hydroxyl groups to a carbonyl group to form a 1,1-diol derivative in which one of the two oxygen atoms is bound to the surface of the carrier by a covalent bond, and the second oxygen atom is negatively charged or is part of a hydroxyl group, leads to the formation of a carrier with a modified surface capable of reacting with activators or precursor compounds of activators to form a covalent bond between the metal atom of the activator and the oxygen atom of the 1,1-diol derivative not bound to the surface of the carrier.

[0016] The described sequence of transformations, as it turned out, can be used to create activators immobilized on the surface of an inorganic oxide carrier using covalent bonds.

[0017] In addition, the inventors have discovered that the solid support obtained in this manner, containing an immobilized activator bound to the surface of the support through a 1, 1-diol derivative in which one of the two oxygen atoms is bound to the surface of the support by a covalent bond and the second oxygen atom is bound to a metal atom of the activator, is capable of activating precatalysts with the formation of olefin polymerization catalysts that, in comparison with catalysts activated by silica gel-based supports containing an immobilized activator, the metal atom in which is directly bound to an oxygen atom of the surface, have a higher activity and form a polymer with a higher molecular weight with a narrow molecular weight distribution (MWD) and a more uniform particle morphology.

[0018] Thus, in one aspect, the invention relates to a compound of general formula (I):

[0019] support - O - A (I),

[0020] where support is a solid substrate of inorganic oxide; A independently represent a functional group of general formula (II) bound to an oxygen atom of the substrate surface:

[0021] [C(R 1 )(R 2 )–O–ML n ] z– (Ct y+ ) z / y (II), where R 1 and R 2 independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, halogen-substituted alkyl, halogen-substituted cycloalkyl, and halogen-substituted aryl, wherein at least one of the R groups 1 and R 2 is a polyfluorinated alkyl, polyfluorinated cycloalkyl, or polyfluorinated aryl, wherein R 1 and R 2 can be linked covalently to each other to form a cycle;

[0022] M is selected from the group consisting of an atom of aluminum, gallium, boron, a transition metal of group 3, and a lanthanide;

[0023] L represent identical or different ligands in the coordination sphere of the M atom; moreover, any ligands L can be linked by covalent bonds to each other;

[0024] n is 2, 3, or 4;

[0025] z is 0 or 1;

[0026] in this case, when z is equal to 0, Ct y+ is absent, and when z is 1, Ct y+ is a cation capable of converting a neutral transition metal complex into a cationic complex capable of catalyzing the polymerization of olefins, with a charge y, where y is 1 or 2;

[0027] in this case, any functional groups A can be linked by covalent bonds to each other.

[0028] According to another aspect, the invention relates to a compound of general formula (VI):

[0029] support - O - A' (VI),

[0030] where support is as defined above;

[0031] A' independently represent a functional group of general formula (VII) bound to an oxygen atom of the substrate surface:

[0032] [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y ​​(VII),

[0033] where R 1 , R 2 , M, L, p, y are as defined above;

[0034] Ct' y+ is a cation with a charge y, selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, and an R cation 5 mNH4-m + ,

[0035] where R 5 independently selected from the group consisting of alkyl, cycloalkyl optionally substituted with one or more hydrocarbyl groups, and aryl optionally substituted with one or more hydrocarbyl groups or a halogen atom, m is 0, 1, 2, 3 or 4,

[0036] in this case, any functional groups A' can be linked by covalent bonds to each other.

[0037] In another aspect, the invention relates to a method for preparing a compound of general formula (I) or general formula (VI), comprising the following steps:

[0038] (1) modification of the substrate surface of general formula (VIII):

[0039] support-(OHi- z ) z '(Ct' ' y+ )z / y (VIII),

[0040] where support, z and y are as defined above;

[0041] Ct' ,у+ represents Ct y+ or Ct' y+ , as defined above;

[0042] by reaction with a carbonyl compound of general formula (IX):

[0043] (R 1 )(R 2 )C=O (IX),

[0044] where R 1 and R 2 are as defined above;

[0045] with the formation of 1,1-diols derivatives of the general formula (X):

[0046] support-O-[C(R 1 )(R 2 )-OH ( iz)] z '(Ct' ,y+ )z / y(X);

[0047] (2) reacting 1,1-diols of general formula (X) with a compound containing at least one ML bond, where M and L are as defined above;

[0048] with the formation of a compound of general formula (I) or (VI).

[0049] In another aspect, the invention relates to the use of a compound of general formula (I) as a solid activating support for an olefin polymerization catalyst.

[0050] In another aspect, the invention relates to an olefin polymerization catalyst formed by the interaction of a compound of general formula (I) and a precatalyst containing a neutral or cationic transition metal complex.

[0051] In another aspect, the invention relates to a catalytic composition comprising the above-described catalyst and an organoaluminum compound.

[0052] In another aspect, the invention relates to a method for producing the above-described olefin polymerization catalyst or the above-described catalytic composition, comprising reacting a compound of general formula (I) with a precatalyst containing a neutral or cationic transition metal complex.

[0053] In another aspect, the invention relates to a method for polymerizing olefins, comprising reacting the above-described catalyst or the above-described catalyst composition with at least one olefin.

[0054] Detailed description of the invention

[0055] Definitions

[0056] All references to the Periodic Table of the Elements in this document will refer to the Periodic Table of the Elements as published and approved by IUPAC.

[0057] Unless otherwise stated, all parts and percentages are by weight.

[0058] The term "comprising" and its derivatives are not intended to exclude the presence of an additional component, step, or operation, whether disclosed herein or not. To avoid any doubt, all compositions claimed herein using the term "comprising" may include any additional additive or excipient, unless otherwise indicated. In contrast, the term "essentially consisting" excludes from the scope of any subsequent listing any other component, step, or operation, except those that do not affect the feasibility of carrying out the invention. The term "consisting of" excludes any component, step, or operation that is not specifically defined or listed. The term "or," unless otherwise indicated, refers to the listed elements individually as well as in any combination.

[0059] Any numerical range specified herein includes all values ​​from the lowest value to the highest value in intervals of one unit, provided that there is a separation of at least 2 units between any lowest value and any highest value. For example, if an amount of a component or a value of a structural or physical property, such as the amount of a component in a mixture, softening point, melt flow index, etc., is specified to lie in a range between 1 and 100, then it is meant that all individual values, such as 1, 2, 3, etc., and all sub-ranges, such as from 1 to 20, from 55 to 70, from 97 to 100, etc., are unambiguously listed in this description. For values ​​less than one, the unit is considered to be 0.0001, 0.001, 0.01, or 0.1, as appropriate.These are only examples of what is specifically intended, and all possible combinations of numerical values ​​between the lowest value and the highest value listed should be considered as expressly stated in this application. In other words, any numerical range cited in this document includes any value or subrange within the stated range.

[0060] The term "composition" as used herein includes a mixture of materials that make up the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0061] The term "polymer" as used herein refers to a macromolecular compound containing repeating structural units that are monomers. "Polymer" includes homopolymers and copolymers.

[0062] The term "olefin" as used herein means an alkene.

[0063] The term "olefin-based polymer" or "polyolefin" refers to a polymer containing, in polymerized form, a major weight percentage of an olefin, such as ethylene or propylene, based on the total weight of the polymer. Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers.

[0064] The term "ethylene-based polymer" as used herein means a polymer that comprises a major weight percentage of polymerized ethylene monomer (based on the total weight of polymerizable monomers), and may optionally include at least one polymerized comonomer.

[0065] The term "propylene-based polymer" as used herein refers to a polymer that comprises a major weight percentage of polymerized propylene monomer (based on the total weight of polymerizable monomers), and may optionally include at least one polymerized comonomer.

[0066] The term "polypropylene" as used herein means a polymer of propylene and possibly a comonomer.

[0067] The term "copolymer" as used herein means a polymer prepared from two or more different monomers.

[0068] The term "monomer" as used herein means a chemical compound that can be polymerized.

[0069] As used herein, the term "hydrocarbyl" refers to substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, fused or acyclic compounds, and combinations thereof. Non-limiting examples of suitable alkyl radicals include, for example, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, and aryl.

[0070] The term "alkyl" as used herein means an alkyl group, which is a functional group, or a side chain consisting of carbon and hydrogen atoms that contains only single bonds. The alkyl group may be straight or branched and may be unsubstituted or substituted. Alkyls may contain from 1 to 40 carbon atoms, preferably from 1 to 30 carbon atoms, more preferably from 1 to 20 carbon atoms, even more preferably from 1 to 10 carbon atoms, even more preferably from 1 to 6 carbon atoms. Non-limiting examples of suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl (or 2-methylpropyl), and the like.

[0071] The term "substituted alkyl" as used herein refers to an alkyl as just discussed above, in which one or more (two, three, four or more) hydrogen atoms attached to any carbon atom of the alkyl are replaced with another group, such as a halogen atom, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen atom, haloalkyl, hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, another heteroatom-containing group, and combinations thereof. Suitable substituted alkyls include, for example, benzyl, trifluoromethyl, and the like.

[0072] The term "cycloalkyl" as used herein refers to a saturated cyclic hydrocarbon group. The cycloalkyl group may be substituted or unsubstituted. Cycloalkyls may contain from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms, more preferably from 3 to 6 carbon atoms. Non-limiting examples of cycloalkyl radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

[0073] The term "aryl" as used herein refers to an aromatic substituent that may represent a single aromatic ring or multiple aromatic rings fused together, covalently bonded, or linked by a common group such as a methylene or ethylene group. Aryls may contain from 6 to 20 carbon atoms, preferably from 6 to 10 carbon atoms. The aromatic ring(s) may include phenyl, naphthyl, anthracenyl, and biphenyl, among others.

[0074] The term "substituted aryl" as used herein refers to an aryl group, as just discussed above, in which one or more (two, three, four, or more) hydrogen atoms in the aromatic ring are replaced by another group. Thus, a substituted aryl group also encompasses alkaryl groups, where one or more (two, three, four, or more) hydrogen atoms in the aromatic ring are replaced by alkyl groups, as well as haloaryl groups, in which one or more (two, three, four, or more) hydrogen atoms in the aromatic ring are replaced by halogen atoms.

[0075] The term "carbocycle," as used herein, refers to a cyclic group of carbon atoms. A carbocycle lacks any atoms other than carbon and hydrogen. A carbocycle can be saturated, unsaturated, or aromatic. A carbocycle can contain from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms, and more preferably from 3 to 6 carbon atoms.

[0076] The term "heterocycle" as used herein refers to a cyclic group of carbon atoms and one or more (two, three, four, or more) heteroatoms. Heteroatoms may be F, Cl, Br, I, N, O, P, β, S, or Si. A heterocycle may include from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms, more preferably from 2 to 6 carbon atoms.

[0077] The term "precatalyst" as used herein means a neutral transition metal complex belonging to the classes of metallocenes (bis(cyclopentadienyl) complexes), half-metallocenes (monocyclopentadienyl complexes) or post-metallocenes (non-cyclopentadienyl complexes), which is capable, upon interaction with an activator, of forming a cationic complex that is a catalyst for the polymerization of olefins. The neutral transition metal complex belonging to the class of metallocenes contains at least two cyclopentadienyl ligands, possibly linked by a bridging group. The neutral transition metal complex belonging to the class of half-metallocenes contains one cyclopentadienyl ligand and at least one non-cyclopentadienyl ligand, possibly linked by a bridging group.A neutral transition metal complex belonging to the class of postmetallocenes does not contain cyclopentadienyl ligands and contains at least two non-cyclopentadienyl ligands, possibly linked by a bridging group.

[0078] The term "cyclopentadienyl ligand" as used herein means a metal-bonded, optionally substituted cyclopentadienyl, optionally fused to a saturated or unsaturated carbocycle or heterocycle, and includes, in particular, cyclopentadienyl, indenyl, fluorenyl and cyclopenta[b]thienyl.

[0079] The term "activator" as used herein means a compound capable of reacting with a precatalyst to form a cationic complex that is a catalyst for the polymerization of olefins.

[0080] The terms "halide" or "halogen" as used herein mean an ion selected from the group consisting of fluoride (F⁻), chloride (Cl⁻), bromide (Br⁻), or iodide (I⁻).

[0081] The term "heteroatom" as used herein means an atom other than carbon or hydrogen. However, as used herein, unless otherwise noted, as below, when the expression "one or more heteroatoms" is used, it means one or more of the following: F, Cl, Br, I, N, O, P, B, S, or Si. Thus, a heteroatom also includes halides.

[0082] Unless otherwise specified, when any R group is referred to as "independently selected from" or "independently represents," it means that if more than one of the same R groups is present in the molecule, they may have the same meaning or they may have different meanings. For example, in the compound R2M, where R is independently selected from ethyl or methyl, both R groups may be ethyl, both R groups may be methyl, or one R group may be ethyl and the other R group may be methyl.

[0083] The term "polyhalogenated alkyl (cycloalkyl, aryl, hydrocarbyl)" as used herein means alkyl (cycloalkyl, aryl, hydrocarbyl) containing two or more (three, four, five, six or more) halogen atoms (fluorine, chlorine, bromine, iodine) as substituents, optionally containing one or more (two, three, four or more) substituents selected from the group: alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen atom, haloalkyl, and

[0084] hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, other heteroatom-containing group, and combinations thereof.

[0085] The term "polyfluorinated alkyl (cycloalkyl, aryl, hydrocarbyl)" as used herein means an alkyl (cycloalkyl, aryl, hydrocarbyl) containing two or more (three, four, five, six or more) fluorine atoms as substituents, optionally containing one or more (two, three, four or more) substituents selected from the group: alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen atom, haloalkyl, hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, another heteroatom-containing group, and combinations thereof.

[0086] The present invention is described in more detail below. All embodiments described with respect to one aspect of the present invention are also applicable to other aspects of the present invention, unless otherwise indicated. Furthermore, all references to "one embodiment," "another embodiment," and "another embodiment" do not necessarily refer to different embodiments, but may also be combined with each other within the framework of a single example of embodiment of the invention.

[0087] According to one aspect, the invention relates to a compound of general formula (I):

[0088] support - O - A (I),

[0089] where support is a solid substrate of inorganic oxide; A independently represent a functional group of general formula (II) bound to an oxygen atom of the substrate surface:

[0090] [C(R 1 )(R 2 )–O–ML n ] z– (Ct y+ ) z / y (II),

[0091] where R1 and R 2 independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, halogen-substituted alkyl, halogen-substituted cycloalkyl, and halogen-substituted aryl, wherein at least one of the R groups 1 and R 2 is a polyfluorinated alkyl, polyfluorinated cycloalkyl, or polyfluorinated aryl, wherein R 1 and R 2 can be linked covalently to each other to form a cycle;

[0092] M is selected from the group consisting of an atom of aluminum, gallium, boron, a transition metal of group 3, and a lanthanide; L are the same or different ligands in the coordination sphere of the atom M; and any ligands L may be covalently bonded to each other;

[0093] n is 2, 3, or 4;

[0094] z is 0 or 1;

[0095] in this case, when z is equal to 0, Ct y+ is absent, and when z is 1, Ct y+is a cation capable of converting a neutral transition metal complex into a cationic complex capable of catalyzing the polymerization of olefins, with a charge y, where y is 1 or 2;

[0096] in this case, any functional groups A can be linked by covalent bonds to each other.

[0097] In one incarnation, each of R 1 and R 2 independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, halogen-substituted alkyl, halogen-substituted cycloalkyl, and halogen-substituted aryl, wherein at least one of the R groups 1 and R 2 is a polyfluorinated alkyl, polyfluorinated cycloalkyl, or polyfluorinated aryl, wherein R 1 and R 2 can be linked covalently to each other to form a cycle.

[0098] In one incarnation R 1 represents a hydrogen atom.

[0099] In one incarnation R 1is alkyl, preferably C1-C20 linear or branched alkyl, more preferably C1-C10 linear or branched alkyl, for example C1-C6 linear or branched alkyl. In particular, R 1 may be methyl, ethyl, propyl, propyl, butyl, pentyl, or hexyl.

[0100] In another incarnation of R 1 is cycloalkyl, preferably C3-C10 cycloalkyl, more preferably C3-C6 cycloalkyl. In particular, R 1 can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

[0101] In another incarnation of R 1 is aryl. Preferably R 1 represents C6-C6 aryl, more preferably Ce-C1 aryl, most preferably R 1 is phenyl.

[0102] In another incarnation of R 1 is a halogen-substituted alkyl. In particular, R 1may be a C1-C20 linear or branched alkyl, more preferably a C1-C10 linear or branched alkyl, such as a C1-C6 linear or branched alkyl, substituted by one or more (two, three, four or more) halogen atoms, where the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In particular, R 1 may be fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, trichloromethyl, tribromomethyl, chlorodifluoromethyl, bromodifluoromethyl, iododifluoromethyl, perfluoroethyl, perfluoropropyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, perfluoroisopropyl, perfluoro-1-propen-1-yl, perfluorobutyl, perfluoroisobutyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoropentyl, perfluorohexyl.

[0103] In another incarnation of R 1 is a halogen-substituted cycloalkyl. In particular, R 1may be C3-C10 cycloalkyl, more preferably C3-C6 cycloalkyl, for example C3-C6 cycloalkyl substituted by one or more (two, three, four or more) halogen atoms, where the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In particular, R 1 may be 2,2-difluorocyclopropyl, perfluorocyclopropyl, 2,2-difluorocyclobutyl, 2,2,3,3-tetrafluorocyclobutyl, perfluorocyclobutyl, 2,2-difluorocyclopentyl, 3,3-difluorocyclopentyl, perfluorocyclopentyl, 1-fluorocyclohexyl, 1-chlorocyclohexyl, 1-bromocyclohexyl, 1-iodocyclohexyl, 2,2-difluorocyclohexyl, 3,3-difluorocyclohexyl, 4,4-difluorocyclohexyl, perfluorocyclohexyl.

[0104] In another incarnation of R 1 is a halogen-substituted aryl. In particular, R 1may be C6-C6 aryl, more preferably C6-C10 aryl, most preferably phenyl, substituted with one or more (two, three, four or more) halogen atoms, wherein the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In particular, R 1 may be 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2,3,5,6-tetrafluorophenyl, perfluorophenyl, 1-perfluoronaphthyl, 2-perfluoronaphthyl, 2-(perfluorophenyl)-3,4,5,6-tetrafluorophenyl.

[0105] In one incarnation R 2 represents a hydrogen atom.

[0106] In one incarnation R 2 is alkyl, preferably C1-C20 linear or branched alkyl, more preferably Ci-Cio linear or branched alkyl, for example Ci-C6 linear or branched alkyl. In particular, R 2 may be methyl, ethyl, propyl, butyl, pentyl, or hexyl.

[0107] In another incarnation of R 2 is cycloalkyl, preferably C3-C10 cycloalkyl, more preferably C3-C6 cycloalkyl. In particular, R 2 may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. In another embodiment, R 2 is aryl. Preferably R 2 represents C6-C6 aryl, more preferably C6-C1 aryl, most preferably R 2 is phenyl.

[0108] In another incarnation of R 2 is a halogen-substituted alkyl. In particular, R 2 may be a C1-C20 linear or branched alkyl, more preferably a C1-C10 linear or branched alkyl, such as a C1-C6 linear or branched alkyl, substituted by one or more (two, three, four or more) halogen atoms, where the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In particular, R 2may be fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, trichloromethyl, tribromomethyl, chlorodifluoromethyl, bromodifluoromethyl, iododifluoromethyl, perfluoroethyl, perfluoropropyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, perfluoroisopropyl, perfluoro-1-propen-1-yl, perfluorobutyl, perfluoroisobutyl, perfluoro-t-butyl, perfluoro-tert-butyl, perfluoropentyl, perfluorohexyl.

[0109] In another incarnation of R 2 is a halogen-substituted cycloalkyl. In particular, R 2 may be C3-C10 cycloalkyl, more preferably C3-C6 cycloalkyl, for example C3-C6 cycloalkyl substituted by one or more (two, three, four or more) halogen atoms, where the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In particular, R 2may be 2,2-difluorocyclopropyl, perfluorocyclopropyl, 2,2-difluorocyclobutyl, 2,2,3,3-tetrafluorocyclobutyl, perfluorocyclobutyl, 2,2-difluorocyclopentyl, 3,3-difluorocyclopentyl, perfluorocyclopentyl, 1-fluorocyclohexyl, 1-chlorocyclohexyl, 1-bromocyclohexyl, 1-iodocyclohexyl, 2,2-difluorocyclohexyl, 3,3-difluorocyclohexyl, 4,4-difluorocyclohexyl, perfluorocyclohexyl.

[0110] In another incarnation of R 2 is a halogen-substituted aryl. In particular, R 2 may be C6-C6 aryl, more preferably C6-C10 aryl, most preferably phenyl, substituted with one or more (two, three, four or more) halogen atoms, wherein the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In particular, R 2may be 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2,3,5,6-tetrafluorophenyl, perfluorophenyl, 1-perfluoronaphthyl, 2-perfluoronaphthyl, 2-(perfluorophenyl)-3,4,5,6-tetrafluorophenyl.

[0111] According to one embodiment, at least one of the groups R 1 and R 2 is a polyfluorinated alkyl. In particular, at least one of the R groups 1 and R 2 may be a polyfluorinated C1-C20 linear or branched alkyl, more preferably C1-C10 linear or branched alkyl, such as C1-C6 linear or branched alkyl. In particular, at least one of the R groups 1 and R 2 may be perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoroisobutyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoropentyl, or perfluorohexyl.

[0112] According to one embodiment, at least one of the groups R 1 and R 2 is a polyfluorinated cycloalkyl. In particular, at least one of the R groups 1 and R 2 may be a polyfluorinated C3-C10 cycloalkyl, more preferably C3-C6 cycloalkyl. In particular, at least one of the R groups 1 and R 2 may be perfluorocyclopropyl, perfluorocyclobutyl, perfluorocyclopentyl, or perfluorocyclohexyl.

[0113] According to another embodiment, at least one of the groups R 1 and R 2 is a polyfluorinated aryl. In particular, at least one of the R groups 1 and R 2 may be a polyfluorinated C6-C6 aryl, more preferably Ce-C1 aryl, most preferably at least one of the R groups 1 and R 2 is a perfluorophenyl.

[0114] According to one embodiment of R 1 and R 2are the same.

[0115] According to another incarnation of R 1 and R 2 can be covalently linked to each other to form a cycle. In particular, R 1 and R 2 may be linked to each other to form a C4-C10 polyfluorinated carbocycle, preferably a C5-C10 polyfluorinated carbocycle.

[0116] According to one embodiment, M is selected from the group consisting of an atom of aluminum, gallium, boron, a Group 3 transition metal, and a lanthanide. Preferably, M is an atom of aluminum, boron, or yttrium. Most preferably, M is an atom of aluminum or boron.

[0117] According to another embodiment, each L independently represents a ligand in the coordination sphere of an atom M.

[0118] In one embodiment, each L is independently a ligand selected from the group consisting of an electron-donating ligand capable of forming a coordinate bond with an atom M, a hydrogen atom, an alkyl, an aryl, a halogen-substituted aryl, a halogen atom, an oxygen atom, OR 3 , OC(O)R 3 and OSO2R 3 , dihydrocarbyl amino groups, bis(dihydrocarbylsilyl) amino groups, bis(trihydrocarbylsilyl) amino groups and cyano groups, where R 3 independently selected from the group consisting of alkyl, aryl, halogen-substituted alkyl, halogen-substituted aryl, and halogen-substituted arylalkyl, each of which may be substituted with alkyl.

[0119] In one embodiment, L represents a hydrogen atom.

[0120] In one embodiment, L is alkyl, preferably C1-C20 linear or branched alkyl, more preferably C1-C10 linear or branched alkyl, such as C1-C6 linear or branched alkyl. In particular, L can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, -butyl, -butyl, pentyl, hexyl, octyl, benzyl, trimethylsilylmethyl.

[0121] In another embodiment, L is aryl. Preferably, L is C6-C6 aryl, more preferably Ce-C6 aryl, most preferably L is phenyl.

[0122] In one embodiment, L is a halogen-substituted aryl. In particular, L may be C6-Cro aryl, more preferably Ce-Cio aryl, most preferably phenyl, substituted with one or more (two, three, four or more) halogen atoms, wherein the halogen is preferably selected from fluorine, chlorine, bromine or iodine. Preferably, L is perfluorophenyl, perchlorophenyl, perbromophenyl, periodophenyl, 1-perfluoronaphthyl, 2-perfluoronaphthyl, 2-(perfluorophenyl)-3,4,5-6-tetrafluorophenyl, 2,4,6-trifluorophenyl, 2,3,5,6-tetrafluorophenyl, 3,5-bis(trifluoromethyl)phenyl. Most preferably, L is perfluorophenyl.

[0123] In one embodiment, L is selected from the group consisting of OR 3 , OC(O)R 3 and OSO2R 3 , where R 3 independently selected from the group consisting of alkyl, aryl, halogen-substituted alkyl, halogen-substituted aryl, and halogen-substituted arylalkyl, each of which may be substituted with alkyl. In one embodiment, R3 is alkyl, preferably C1-C20 linear or branched alkyl, more preferably C1-C10 linear or branched alkyl, for example C1-Ce linear or branched alkyl. In particular, R 3 may be methyl, ethyl, propyl, propyl, butyl, pentyl, or hexyl. In another embodiment, R 3 is aryl. Preferably R 3 represents C6-C6 aryl, more preferably Ce-C1 aryl, most preferably R 3 represents phenyl. In another embodiment, R 3 is an aryl substituted by alkyl. In particular, R 3 may be C6-C6 aryl, more preferably C6-C10 aryl, substituted with one or more (two, three, four or more) Ci-C10 alkyls. In another embodiment, R 3 is a halogen-substituted alkyl. In particular, R 3may be a C1-C20 linear or branched alkyl, more preferably a Ci-Cio linear or branched alkyl, such as a C1-C6 linear or branched alkyl, substituted by one or more (two, three, four or more) halogen atoms, where the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In particular, R 3 may be fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, trichloromethyl, tribromomethyl, perfluoroethyl, perfluoropropyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, perfluoroisopropyl, perfluoro-n-butyl, perfluoroisobutyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoropentyl, perfluorohexyl. In another embodiment, R 3 is a halogen-substituted aryl. In particular, R 3may be C6-C6 aryl, more preferably Ce-Cio aryl, most preferably phenyl, substituted with one or more (two, three, four or more) halogen atoms, wherein the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In particular, R 3 may be 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 2,6-difluorophenyl, 2,4,6-trifluorophenyl, 2, 3,5,6-tetrafluorophenyl, perfluorophenyl, 1-perfluoronaphthyl, 2-perfluoronaphthyl, 2-(perfluorophenyl)-3,4,5,6-tetrafluorophenyl. In another embodiment, R 3 is a halogen-substituted aryl substituted by alkyl. In particular, R 3 may be C6-C6 aryl, more preferably C6-C10 aryl, substituted with one or more (two, three, four or more) halogen atoms and one or more (two, three, four or more) Ci-Cio alkyls, wherein the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In another embodiment, R 3is a halogen-substituted arylalkyl. In particular, R 3 may be a C7-C20 arylalkyl, more preferably a C7-C14 arylalkyl, substituted with one or more (two, three, four or more) halogen atoms, wherein the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In another embodiment, R 3 is a halogen-substituted arylalkyl substituted with alkyl. In particular, R 3 may be a C7-C20 arylalkyl, more preferably a C7-C14 arylalkyl, substituted with one or more (two, three, four or more) halogen atoms and one or more (two, three, four or more) Ci-Cio alkyls, where the halogen is preferably selected from fluorine, chlorine, bromine or iodine. In particular, R 3 may be 1,1,1,3,3,3-hexafluoro-2-(-tolyl)propan-2-yl. Preferably R 3 is a polyhalogenated alkyl or polyhalogenated aryl. Most preferably R 3is a polyfluorinated alkyl or polyfluorinated aryl.

[0124] In another embodiment, L is an alkoxy or aryloxy group. In particular, L is a methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, -butoxy, -butoxy, phenoxy group. Preferably, L is an isopropoxy group.

[0125] Furthermore, in another embodiment, L is a halogen-substituted alkoxy or aryloxy group. In particular, L may be selected from the group consisting of C1-C20 alkoxy, more preferably C1-C10 alkoxy, such as C6-C6 alkoxy groups, or C6-C6 aryloxy, more preferably Ce-Cio aryloxy, most preferably phenyloxy group, substituted by one or more (two, three, four or more) halogen atoms, wherein the halogen is preferably selected from fluorine, chlorine, bromine or iodine. Preferably, L is perfluoromethoxy, perfluoroethoxy, perfluoro-n-propoxy, 1,1,1,3,3,3-hexafluoropropane-2-oxy, perfluoroisopropoxy, perfluoro-n-butoxy, perfluoroisobutoxy, perfluoro-sec-butoxy, perfluoro--butoxy, perfluoropentoxy, perfluorohexoxy, perfluorophenyloxy, 1-perfluoronaphthoxy, 2-perfluoronaphthoxy, 2-(perfluorophenyl)-3,4,5,6-tetrafluorophenoxy, 2,4,6-trifluorophenoxy, 2,3,5,6-tetrafluorophenoxy, or 3,5-bis(trifluoromethyl)phenoxy group.

[0126] Most preferably, L is 1,1,1,3,3,3-hexafluoropropane-2-oxy, perfluoro-butoxy and perfluorophenyloxy group.

[0127] In another embodiment, L is a hydrocarboxy group OC(O)R 3 . Preferably, L is OC(O)CH3, OC(O)CgH5, OC(O)CH(CH3)2, OC(O)C(CH3)3, OC(O)C6H5, OC(O)CF3, OC(O)C2F5, OC(O)C6F5.

[0128] In another embodiment, L represents an OSO2R group. 3 . Preferably, L is OSO2CF3, OSO2(-C4F9), OSO2(-C8F 17 ).

[0129] In another embodiment, L is a dihydrocarbyl amino group, a bis(dihydrocarbylsilyl) amino group, or a bis(trihydrocarbylsilyl) amino group. In particular, said ligand is a C2-C20 dialkyl amino group, such as a C2-C10 dialkyl amino group; a C4-C20 bis(dialkylsilyl) amino group, such as a C4-C10 bis(dialkylsilyl) amino group; or a C4-C20 bis(trialkylsilyl) amino group, such as a Ce-Cio bis(trialkylsilyl) amino group. In particular, said ligand is a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, a dibutylamino group, a diisobutylamino group, a bis(dimethylsilyl)amino group, a bis(trimethylsilyl)amino group. Preferably, L is a dimethylamino group.

[0130] In one embodiment, L is a cyano group.

[0131] In one embodiment, L is a halogen atom. In particular, L is selected from the group consisting of F, Cl, Br and I, most preferably F.

[0132] In one embodiment, L is independently selected from electron-donating ligands capable of forming a coordination bond with the M atom. In particular, L can be an alcohol (phenol), an ether, a trihydrocarbylamine, a trihydrocarbylphosphine, an aromatic nitrogen-containing heterocycle, an aromatic oxygen-containing heterocycle, an aromatic sulfur-containing heterocycle, an aryl halide, a tri(C1-C10)alkylaluminum, a di(C1-C10)alkylaluminum hydride.

[0133] In one embodiment, the alcohol (phenol) is a compound of the general formula R 3 OH, where R 3 is as defined above.

[0134] In one embodiment, the ether is a compound of the general formula R 3 2OH, where R 3 is as defined above. In one embodiment, the trihydrocarbylamine is a compound of the general formula R 3 3N, where R 3 is as defined above.

[0135] In one embodiment, the trihydrocarbylphosphine is a compound of the general formula R 3 3P, where R 3 is as defined above.

[0136] In one embodiment, the aryl halide is a compound in which the C6-Cio aryl is bonded to at least one F, Cl, Br, or I atom. Preferably, the aryl halide is a compound in which the Ce aryl is bonded to at least one F or Cl atom.

[0137] An aromatic nitrogen-containing heterocycle is a 5-membered or 6-membered heterocycle, unsubstituted or substituted by one or more Ci-Cio alkyl groups, containing at least one nitrogen atom. In one embodiment, the aromatic nitrogen-containing heterocycle is a 5-membered or 6-membered heterocycle fused with one or two aryls. In particular, the aromatic nitrogen-containing heterocycle is pyrrole, pyrazole, imidazole, triazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, indole, indazole, benzimidazole, benzotriazole, quinoline, isoquinoline, carbazole, acridine, phenazine, phenanthroline. The aromatic oxygen-containing heterocycle is a 5-membered or 6-membered heterocycle, unsubstituted or substituted by one or more Ci-Cio alkyl groups, containing at least one oxygen atom.In one embodiment, the aromatic oxygen-containing heterocycle is a 5-membered or 6-membered heterocycle fused with one or two aryls. In particular, the aromatic oxygen-containing heterocycle is furan, oxazole, isoxazole, oxadiazole, benzoxazole, phenoxazine, benzofuran, dibenzofuran, or phenoxazine.

[0138] An aromatic sulfur-containing heterocycle is a 5-membered or 6-membered heterocycle, unsubstituted or substituted by one or more Ci-Cio alkyl groups, containing at least one sulfur atom. In one embodiment, the aromatic sulfur-containing heterocycle is a 5-membered or 6-membered heterocycle fused with one or two aryls. In particular, the aromatic sulfur-containing heterocycle is thiophene, thiazole, thiadiazole, benzothiophene, benzothiazole, dibenzothiophene, or thianthrene.

[0139] Specific examples of L are isopropanol, perfluoro-butanol, perfluorophenol, diethyl ether, dibutyl ether, tetrahydrofuran, pyridine, quinoline, imidazole, benzimidazole, oxazole, thiazole, pyrazine, pyrimidine, fluorobenzene, 1,2-difluorobenzene, chlorobenzene, anisole, N,N-dimethyl aniline.

[0140] In one embodiment, L represents an oxygen atom.

[0141] In another embodiment, any ligands L are covalently linked to each other.

[0142] In another incarnation of Ct y+ is a cation capable of converting a neutral transition metal complex into a cationic complex capable of catalyzing the polymerization of olefins, with a charge y, where y is 1 or 2. In particular, Ct y+ can be selected from the group consisting of R 4 3C + , R 5 3NH + , R 6 2Al + , ((R 5 3N)2AlR 6 2) + , H(R 5 3N–AlR 6 2)2 + , Where

[0143] R 4 independently represent aryl, optionally substituted with one or more hydrocarbyl groups and / or one or more trihydrocarbylsilyl groups;

[0144] R 5 independently selected from the group consisting of a hydrogen atom, alkyl, cycloalkyl optionally substituted with one or more hydrocarbyl groups, and aryl optionally substituted with one or more hydrocarbyl groups or a halogen atom;R 6 independently selected from the group consisting of a hydrogen atom, alkyl, cycloalkyl optionally substituted with one or more hydrocarbyl groups, aryl optionally substituted with one or more hydrocarbyl groups.

[0145] In one incarnation, R 4 is aryl. Preferably R 4 represents C6-C6 aryl, more preferably Ce-C1 aryl, most preferably R 4 is phenyl.

[0146] In another incarnation of R 4 represents C6-C6 aryl, more preferably Ce-Cio aryl, most preferably phenyl, substituted with one or more (two, three, four or more) alkyls, wherein said alkyl is independently selected from Ci-C6 alkyl, preferably Ci-Cio alkyl, more preferably Ci-C6 alkyl. In another embodiment, R 4 is C6-C6 aryl, more preferably Ce-Cio aryl, most preferably phenyl, substituted with one or more (two, three, four or more) trihydrocarbylsilyl groups, wherein said trihydrocarbylsilyl groups are independently selected from a Ci-C6 alkylsilyl group, preferably a Ci-Cio alkylsilyl, more preferably a Ci-Ce alkylsilyl group. Preferably, R 4independently represents phenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 2-hexylphenyl, 3-hexylphenyl, 4-hexylphenyl, 4-t / het-butylphenyl, 4-trimethylsilylphenyl, 3,5-bis(triethylsilyl)phenyl. Most preferably, R 4 is phenyl.

[0147] In another incarnation, R 5 represents a hydrogen atom; or alkyl, preferably C1-C40 linear or branched alkyl, more preferably C14-C20 linear or branched alkyl, for example Cie-Cis linear or branched alkyl; or cycloalkyl, preferably C3-Cro cycloalkyl, in particular C3-Cio cycloalkyl; or aryl, preferably C6-Cro aryl, more preferably Ce-Cio aryl, most preferably phenyl. In another embodiment, R 5is C3-Cro cycloalkyl, in particular C3-Cio cycloalkyl, substituted by one or more (two, three, four or more) alkyls, wherein said alkyl is independently selected from C1-C3 alkyl, preferably C1-C1 alkyl, more preferably C1-C6 alkyl; or aryl, preferably C6-C1 aryl, more preferably Ce-C1 aryl, most preferably phenyl, substituted by one or more (two, three, four or more) alkyls, wherein said alkyl is independently selected from C1-C3 alkyl, preferably C1-C1 alkyl, more preferably C1-C6 alkyl; or aryl, preferably C6-C1 aryl, more preferably C6-C1 aryl, most preferably phenyl, substituted by one or more (two, three, four or more) halogen atoms, wherein said halogen atom is selected from an atom of F, Cl, Br and I. Preferably, R 5is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, em p-butyl, tert-butyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 1-naphthyl, 2-naphthyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-fluorophenyl, 4-bromophenyl, 4-iodophenyl, or perfluorophenyl.

[0148] In one incarnation, R 6 represents a hydrogen atom; or alkyl, preferably C1-C40 linear or branched alkyl, more preferably C14-C20 linear or branched alkyl, for example Cie-Cis linear or branched alkyl; or cycloalkyl, preferably C3-C20 cycloalkyl, in particular C3-C10 cycloalkyl; or aryl, preferably C6-C6 aryl, more preferably Ce-C10 aryl, most preferably phenyl. In another embodiment, R 6is C3-Cro cycloalkyl, in particular C3-Cio cycloalkyl, substituted by one or more (two, three, four or more) alkyls, wherein said alkyl is independently selected from C1-C3 alkyl, preferably C1-C1 alkyl, more preferably C1-C6 alkyl; or aryl, preferably C6-C6 aryl, more preferably Ce-C1 aryl, most preferably phenyl, substituted by one or more (two, three, four or more) alkyls, wherein said alkyl is independently selected from C1-C3 alkyl, preferably C1-C1 alkyl, more preferably C1-C6 alkyl. Preferably R 6 represents a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, em p-butyl, / 77 / 2C / 77-butyl, hexyl, octyl, phenyl.

[0149] Preferably, Ct y+ selected from the group consisting of triphenylmethylium, N,N-dimethylanilinium, methyldi(octadecyl)ammonium, methyl(octadecyl)(hexadecyl)ammonium, methyldi(hexadecyl)ammonium, methyldi(tetradecyl)ammonium, ((PhNMe2)2AlBu2) +and H(PhNMe2-AlzBu2)2 + .

[0150] Most preferably, Ct y+ selected from the group consisting of triphenylmethylium, N,N-dimethylanilinium, / BrigAl + , ((РйММег)гА1 / Ви2) + and H(PhNMe2-A1ZBU2)2 + .

[0151] According to one embodiment, the functional group A is a functional group of general formula (III):

[0152] C(R 1 )(R 2 )–O–MX2Q m (III), where M, R 1 and R 2 are as described above;

[0153] each X independently represents a ligand selected from the group consisting of a hydrogen atom, alkyl, aryl, halogen-substituted aryl, halogen atom, oxygen atom, OR 3 , OC(O)R 3 and OSO2R 3 ;

[0154] where R 3 is as defined above;

[0155] each Q is independently selected from electron-donating ligands capable of forming a coordination bond with the M atom;

[0156] m is 0, 1 or 2;

[0157] in this case, any of X and / or Q can be covalently linked to each other to form a cycle.

[0158] In one embodiment, each X is independently selected from the group consisting of hydrogen, alkyl, aryl, halogen-substituted aryl, halogen, oxygen, OR 3 , OC(O)R 3 and OSO2R 3 , where R 3 is as defined above.

[0159] In one embodiment, X is selected from the group consisting of a hydrogen atom, an oxygen atom, or a halogen atom such as fluorine, chlorine, bromine, or iodine.

[0160] In one embodiment, X is alkyl, preferably C1-C20 linear or branched alkyl, more preferably C1-C10 linear or branched alkyl, such as C1-C6 linear or branched alkyl. In particular, X may be methyl, ethyl, propyl, butyl, pentyl, or hexyl.

[0161] In another embodiment, X is aryl. Preferably, X is C6-C6 aryl, more preferably Ce-C6 aryl, most preferably X is phenyl.

[0162] In another embodiment, X is a halogen-substituted aryl. In particular, X may be C6-C6 aryl, more preferably Ce-C10 aryl, most preferably phenyl, substituted by one or more (two, three, four or more) halogen atoms, wherein the halogen is preferably selected from fluorine, chlorine, bromine or iodine. Preferably, X is a polyhalogenated aryl. In particular, X may be perfluorophenyl, perchlorophenyl, perbromophenyl or periodophenyl.

[0163] In yet another embodiment, X is selected from the group consisting of OR 3 , OC(O)R 3 and OSO2R 3 , where R 3 is as defined above.

[0164] In one embodiment, Q is independently selected from electron-donating ligands capable of forming a coordination bond with the M atom. In particular, Q can be an alcohol (phenol), an ether, a trihydrocarbylamine, a trihydrocarbylphosphine, an aromatic nitrogen-containing heterocycle, an aromatic oxygen-containing heterocycle, an aromatic sulfur-containing heterocycle, an aryl halide, a tri(C1-C10)alkylaluminum, a di(C1-C10)alkylaluminum hydride.

[0165] In one embodiment, the alcohol (phenol) is a compound of the general formula R 3 OH, where R 3 is as defined above.

[0166] In one embodiment, the ether is a compound of the general formula R 3 2OH, where R 3 is as defined above.

[0167] In one embodiment, the trihydrocarbylamine is a compound of the general formula R 3 sN, where R 3 is as defined above.

[0168] In one embodiment, the trihydrocarbylphosphine is a compound of the general formula R 3 3P, where R 3 is as defined above.

[0169] In one embodiment, the aryl halide is a compound in which the C6-Cio aryl is bonded to at least one F, Cl, Br, or I atom. Preferably, the aryl halide is a compound in which the Ce aryl is bonded to at least one F or Cl atom.

[0170] An aromatic nitrogen-containing heterocycle is a 5-membered or 6-membered heterocycle, unsubstituted or substituted by one or more Ci-Cio alkyl, containing at least one nitrogen atom. In one embodiment, the aromatic nitrogen-containing heterocycle is a 5-membered or 6-membered heterocycle fused with one or two aryls. In particular, the aromatic nitrogen-containing heterocycle is pyrrole, pyrazole, imidazole, triazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, indole, indazole, benzimidazole, benzotriazole, quinoline, isoquinoline, carbazole, acridine, phenazine, phenanthroline.

[0171] An aromatic oxygen-containing heterocycle is a 5-membered or 6-membered heterocycle, unsubstituted or substituted by one or more Ci-Cio alkyl groups, containing at least one oxygen atom. In one embodiment, the aromatic oxygen-containing heterocycle is a 5-membered or 6-membered heterocycle fused with one or two aryls. In particular, the aromatic oxygen-containing heterocycle is furan, oxazole, isoxazole, oxadiazole, benzoxazole, phenoxazine, benzofuran, dibenzofuran, or phenoxazine.

[0172] An aromatic sulfur-containing heterocycle is a 5-membered or 6-membered heterocycle, unsubstituted or substituted by one or more Ci-Cio alkyl groups, containing at least one sulfur atom. In one embodiment, the aromatic sulfur-containing heterocycle is a 5-membered or 6-membered heterocycle fused with one or two aryls. In particular, the aromatic sulfur-containing heterocycle is thiophene, thiazole, thiadiazole, benzothiophene, benzothiazole, dibenzothiophene, or thianthrene.

[0173] Specific examples of Q are isopropanol, perfluoro-tert-butanol, perfluorophenol, diethyl ether, dibutyl ether, tetrahydrofuran, pyridine, quinoline, imidazole, benzimidazole, oxazole, thiazole, pyrazine, pyrimidine, fluorobenzene, 1,2-difluorobenzene, chlorobenzene, anisole, N,N-dimethyl aniline.

[0174] Preferably Q is selected from fluorobenzene, diethyl ether, perfluorophenol and perfluoro-tert-butanol.

[0175] Most preferably, Q is perfluoro-tert-butanol. In another embodiment, any of X and / or Q are covalently bonded to each other to form a ring comprising an atom M and consisting of 3 to 10 atoms. In a preferred embodiment, any of X and Q are bonded to each other to form a ring comprising an atom M and consisting of 3 to 6 atoms.

[0176] According to another embodiment, the functional group A is a functional group of general formula (IV):

[0177] [CCR^ RyO-MXsJ'CCt^i / y CIV),

[0178] where M, R 1 , R 2 , X, Ct y+ and y are as defined above;

[0179] in this case, any of the X can be covalently linked to each other to form a cycle.

[0180] In yet another embodiment, any one of X and / or Q forms a coordinate bond with at least one other atom M' that is not covalently bonded to the solid support and belongs to the same group as the atom M.

[0181] In another embodiment, the functional group A is a functional group of general formula (V):

[0182] C(R 1 )(R 2 )–O–(alkylaluminoxane) (V)

[0183] where R 1 and R 2 are as described above. In formula (V), the alkylaluminoxane may be C1-C20 alkylaluminoxane, preferably C1-C10 alkylaluminoxane, more preferably Ci-C6 alkylaluminoxane. In particular, in formula (V), the alkylaluminoxane is methylaluminoxane, isobutylaluminoxane, tetraisobutylaluminoxane, hexaisobutylaluminoxane, methylisobutylaluminoxane. Preferably, in formula (V), the alkylaluminoxane is methylaluminoxane.

[0184] In one embodiment, the solid inorganic oxide support is silica gel, alumina, or aluminosilicate. Preferably, the inorganic oxide support has a surface hydroxyl group content of 0.4-1.2 mmol / g. Most preferably, the support is silica gel containing surface hydroxyl groups at a concentration of 0.6-0.8 mmol / g.

[0185] Specific embodiments of the functional groups A of the compound of general formula (I) are, for example:

[0186] O–C(CF3)2–O–Al(*tert*-C4F9O)2

[0187]

[0188] O–C(CF3)2–O–Al(*tert*-C4F9O)(*tert*-C4F9OH)

[0189] O-C(CP3)2-O-A1(ot / ?et-C4p9O)2(g / zo-C3H7OH)

[0190] OC(CF3)2-O-Al(m / 2em-C4F9O)2(PhF)

[0191] OC(CF3)2-O-A1(C6F5O)2

[0192] OC(CF3)2-O-Al(C6F5O)2(m / ?em-C4F9OH)

[0193] O-C(SR3)2-O-A1(SbP5O)2(g / zo-SzH7OH)

[0194] OC(CF3)2-O-Al(C6F5O)2(PhF)

[0195] OC(CF3)2-O-A1(C6F5)2

[0196] OC(CF3)2-O-AlF(m / 2em-C4F9O)

[0197] O–C(CF3)2–O–AlF(*tert*-C4F9O)(*tert*-C4F9OH)

[0198] OC(CF3)2-O-AlF(m / ?em-C4F9O)(w3o-C3H7OH)

[0199] OC(CF3)2-O-AlF(m / 2em-C4F9O)(PhF)

[0200] O-C(CPz)g-O-B (m / ?em-C4F9O)2

[0201] OC(CF3)2-OB (C6F5O)2

[0202] OC(CF3)2-OB (C6F5)2

[0203] OC(CF3)2-OY( / 77 / 2C / 77-C4F9O)2

[0204] OC(CF3)2-OY(C6F5O)2

[0205] OC(CF3)2-OY(C6F5O)2( / 77 / 2C / 77-C4F9OH)

[0206] O-C(CPz)2-O-¥(CbP5O)2(g / zo-CzH7OH)

[0207] OC(CF3)(C6F5)-O-AI( / 77 / 2C / 77-C4F9O)2

[0208] O–C(CF3)(C6F5)–O–Al(*tert*-C4F9O)2(*tert*-C4F9OH)

[0209] O-C(CPz)(CbP5)-O-A1(777 / 2et-C4p9O)2(g / zo-CzH7OH)

[0210] OC(CF3)(C6F5)-O-AI( / 7? c / 77-C4F9O)2(PhF)OC(CF3)(C6F5)-O-A1(C6F5O)2

[0211] OC(CF3)(C6F5)-O-Al(C6F5O)2(m / 2em-C4F9OH)

[0212] О-С(СРз)(СбР5)-О-А1(СбР5О)2(г / зо-СзН7ОН)

[0213] OC(CF3)(C6F5)-O-Al(C6F5O)2(PhF)

[0214] OC(CF3)(C6F5)-O-A1(C6F5)2

[0215] OC(CF3)(C6F5)-O-AlF(m / 2em-C4F9O)

[0216] O–C(CF3)(C6F5)–O–AlF(*tr*-C4F9O)(*tr*-C4F9OH) OC(CF3)(C6F5)-O-AlF(m / 2em-C4F9O)(w3o-C3H7OH) OC(CF3)(C6F5)-O-AlF(m / 2em-C4F9O)(PhF)

[0217] OC(CF3)(C6F5)-OB (m / ?em-C4F9O)2

[0218] OC(CF3)(C6F5)-OB(C6F5O)2

[0219] OC(CF3)(C6F5)-OB(C6F5)2

[0220] OC(CF3)(C6F5)-OY(m / 2em-C4F9O)2

[0221] OC(CF3)(C6F5)-OY(C6F5O)2

[0222] OC(CF3)(C6F5)-OY(C6F5O)2(m / ?em-C4F9OH)

[0223] OC(CF3)(C6F5)-OY(C6F5O)2(W3O-C3H7OH)

[0224] OC(w3o-C3F7)2-O-Al(m / ?em-C4F9O)2

[0225] O–C(*iso*-C3F7)2–O–Al(*tert*-C4F9O)2(*tert*-C4F9OH) O-C(r / zo-C3P7)2-O-Al(m / 2et-C4p9O)2(r / zo-C3H7OH) OC(w3o-C3F7)2-O-Al(m / ?em-C4F9O)2(PhF)

[0226] OC(W3O-C3F7)2-O-A1(C6F5O)2

[0227] O-C(r / zo-CzR7)2-O-A1(CbR5O)2(t / 2et-C4r9OH)

[0228] O-C(g / zo-CzR7)2-O-A1(CzR5O)2(g / zo-CzN7OH)

[0229] OC(w3o-C3F7)2-O-Al(C6F5O)2(PhF)

[0230] OC(W3O-C3F7)2-O-A1(C6F5)2

[0231] O–C(*iso*-C3F7)2–O–AlF(*tert*-C4F9O)

[0232] O–C(*iso*-C3F7)2–O–AlF(*tert*-C4F9O)(*tert*-C4F9OH) OC(w3o-C3F7)2-O-AlF(m / 2em-C4F9O)(w3o-C3H7OH) OC(w3o-C3F7)2-O-AlF(m / ?em-C4F9O)(PhF)

[0233] O-C(g / zo-SzR7)g-O-V (m / ?em-C4F9O)2

[0234] OC(W3O-C3F7)2-OB(C6F5O)2

[0235] OC(W3O-C3F7)2-OB(C6F5)2

[0236] O–C(*iso*-C3F7)2–O–Y(*tert*-C4F9O)2

[0237] OC(W3O-C3F7)2-OY(C6F5O)2O-C(w3o-C3F7)2-OY(C6F5O)2(m / ?em-C4F9OH)

[0238] OC(W3O-C3F7)2-OY(C6F5O)2(W3O-C3H7OH)

[0239] O-CH(C4F9)-O-Al(m / 2em-C4F9O)2

[0240] O–CH(C4F9)–O–Al(*tr*-C4F9O)(*tr*-C4F9OH) O-CH(C4F9)-O-Al(m / 2em-C4F9O)2(w3o-C3H7OH) O-CH(C4F9)-O-Al(m / 2em-C4F9O)2(PhF)

[0241] O-CH(C4F9)-O-A1(C6F5O)2

[0242] O-CH(C4F9)-O-Al(C6F5O)2(m / ?em-C4F9OH)

[0243] O-CH(C4F9)-O-A1(C6F5O)2(W3O-C3H7OH)

[0244] O-CH(C4F9)-O-Al(C6F5O)2(PhF)

[0245] O-CH(C4F9)-O-A1(C6F5)2

[0246] O-CH(C4F9)-O-AlF(m / 2em-C4F9O)

[0247] O–CH(C4F9)–O–AlF(*tr*-C4F9O)(*tr*-C4F9OH) O-CH(C4F9)-O-AlF(m / 2em-C4F9O)(w3o-C3H7OH) O-CH(C4F9)-O-AlF(m / 2em-C4F9O)(PhF)

[0248] O–CH(C4F9)–O–B (*трет*-C4F9O)2

[0249] O-CH(C4F9)-OB(C6F5O)2

[0250] O-CH(C4F9)-OB(C6F5)2

[0251] O-CH(C4F9)-OY(m / 2em-C4F9O)2

[0252] O-CH(C4F9)-OY(C6F5O)2

[0253] O-CH(C4F9)-OY(C6F5O)2( / 77 / 2C / 77-C4F9OH)

[0254] O-CH(C4F9)-OY(C6F5O)2(W3O-C3H7OH)

[0255] OC(CF3)2-O-Al(m / 2em-C4F9O)2(PhNMe2)

[0256] OC(CF3)2-O-Al( / 77 / 2e777-C4F9O)2(C6F5OH)

[0257] OC(CF3)2-O-Al( / 77 / 2C / 77-C4F9O)2(Et2O)

[0258] O–C(CF3)2–O–Al(C 10 F7)2

[0259] OC(CF3)2-O-A1(2-(C6F5)C6F4)2

[0260] О-С(СРз)2-О-А1(3,5-(СРз)2-СбНз)2

[0261] O–C(CF3)2–O–B(C 10 F7)2

[0262] OC(CF3)2-OB(2-(C6F5)C6F4)2

[0263] О-С(СРз)2-О-В(3,5-(СРз)2-СбНз)2

[0264] О-С(СРз)2-О-А1((4-Ме-СбН4)С(СРз)2О)2

[0265] OC(CF3)2-O-A1((CF3)2CHO)2

[0266] OC(CF3)2-O-A1(OC(CF3)2C(CF3)2O)O-CH(C6F5)-O-Al(m / ?em-C4F9O)2

[0267] OC(CF3)(CF2Cl)-O-Al(m / ?em-C4F9O)2

[0268] OC(CF3)2-O-Ga(m / 2em-C4F9O)2

[0269] OC(CF3)г-О-метилалюмоксан

[0270] OC(CF3)2-O-Al(m / 2em-C4F9O)(C6F5O)

[0271] OC(CF3)2-O-Al(m / 2em-C4F9O)2FAl(m / 2em-C4F9O)2

[0272] OC(CF3)2-O-Al(m / 2em-C4F9O)2(CN)Al(m / 2em-C4F9O)2

[0273] OC(CF3)2-O-Al(m / 2em-C4F9O)2(OH)Al(m / 2em-C4F9O)2

[0274] OC(CF3)2-O-Al(m / 2em-C4F9O)2(CF3COO)Al(m / 2em-C4F9O)2 OC(CF3)2-O-Al(m / 2em-C4F9O)2(CF3SO3)Al(m / 2em-C4F9O)2 О-С(СР3)2-О-А1(т / 2ет-С4р9O)2(имидазолил)А1(т / 2ет-С4р9O)г O

[0275]

[0276] -C(CF3)2-O-Al(m / ?em-C4F9O)3-Ph3C +

[0277] OC(CF3)2-O-Al(m / 2em-C4F9O)3-PhNHMe2 +

[0278] OC(CF3)2-O-Al(m / 2em-C4F9O)3“zBu2Al +

[0279] OC(CF3)2-O-Al(C6F5O)3-Ph3C +

[0280] OC(CF3)2-O-Al(C6F5O)3-PhNHMe2 +

[0281] OC(CF3)2-O-A1(C6F5O)3-Bu2Al +

[0282] OC(CF3)2-O-Al(C6F5)3-Ph3C +

[0283] OC(CF3)2-O-Al(C6F5)3-PhNHMe2 +

[0284] OC(CF3)2-O-A1(C6F5)3-Bu2Al +

[0285] OC(CF3)2-O-Al(z / 3o-C3H7O)(z7z / 2ezzz-C4F9O)2-Ph3C +

[0286] OC(CF3)2-O-Al(z / 3o-C3H7O)(z7z / 2ezzz-C4F9O)2'PhNHMe2 + OC(CF3)2-O-Al(z / 3o-C3H7O)(z7z / 2ezzz-C4F9O)2-zBu2Al +

[0287] O

[0288]

[0289] -C(CF3)2-OB(zzz / ?ez7z-C4F9O)3-Ph3C +

[0290] OC(CF3)2-OB(zzz / 2ezzz-C4F9O)3-PhNHMe2 +

[0291] OC(CF3)2-OB(z7z / 2ezzz-C4F9O)3-zBu2 Al +

[0292] OC(CF3)2-OB(C6F5O)3-Ph3C +

[0293] OC(CF3)2-OB(C6F5O)3-PhNHMe2 +

[0294] OC(CF3)2-OB(C6F5O)3-Bu2Al +

[0295] OC(CF3)2-OB(C6F5)3-Ph3C +

[0296] OC(CF3)2-OB(C6F5)3-PhNHMe2 +

[0297] OC(CF3)2-OB(C6F5)3-Bu2Al +

[0298] OC(CF3)2-OY(z7z / 2ezzz-C4F9O)3-Ph3C +

[0299] OC(CF3)2-OY(z7z / 2ezzz-C4F9O)3-PhNHMe2 + OC(CF3)2-OY(m / ?em-C4F9O)3'2-MePhNHMe2 +

[0300] OC(CF з)г-О-¥ (and-C F 9О)з“ / Ви2 Al +

[0301] OC(CF3)2-OY(C6F5O)3-Ph3C +

[0302] OC(CF3)2-OY(C6F5O)3-PhNHMe2 +

[0303] OC(CF3)2-OY(C6F5O)3-7BU2A1 +

[0304] OC(CF3)2-OY(C6F5)3-Ph3C +

[0305] OC(CF3)2-OY(C6F5)3-PhNHMe2 +

[0306] OC(CF3)2-OY(C6F5)3-Bu2Al +

[0307] OC(CF3)2-OY(w3o-C3H7O)(m / ?em-C4F9O)2-Ph3C +

[0308] OC(CF3)2-OY(w3o-C3H7O)(m / 2em-C4F9O)2-PhNHMe2 +

[0309] O–C(CF3)2–O–Y(*изо*-C3H7O)(*трет*-C4F9O)2–Bu2Al +

[0310] O

[0311]

[0312] -C(CF3)(C6F5)-O-Al(zzz / ?ezzz-C4F9O)3-Ph3C +

[0313] OC(CF3)(C6F5)-O-Al(zzz / ?ezzz-C4F9O)3-PhNHMe2 +

[0314] OC(CF3)(C6F5)-O-Al(zzz / 2ezzz-C4F9O)3-zBu2Al +

[0315] О-С(СРз)(СбР5)-О-А1(СбР5О)з-РНзС +

[0316] OC(CF3)(C6F5)-O-Al(C6F5O)3-PhNHMe2 +

[0317] OC(CF3)(C6F5)-O-A1(C6F5O)3-Bu2Al +

[0318] О-С(СРз)(СбР5)-О-А1(СбР5)з-РНзС +

[0319] OC(CF3)(C6F5)-O-Al(C6F5)3-PhNHMe2 +

[0320] OC(CF3)(C6F5)-O-A1(C6F5)3-Bu2Al +

[0321] OC(CF3)(C6F5)-O-Al(z / 3o-C3H7O)(zzz / ?ezzz-C4F9O)2-Ph3C +

[0322] OC(CF3)(C6F5)-O-Al(z / 3o-C3H7O)(zzz / ?ezzz-C4F9O)2-PhNHMe2 + OC(CF3)(C6F5)-O-Al(z / 3o-C3H7O)(zzz / 2ezzz-C4F9O)2“zBu2Al + O

[0323]

[0324] -C(CF3)(C6F5)-OB(zzz / ?ezzz-C4F9O)3-Ph3C +

[0325] OC(CF3)(C6F5)-OB(zzz / ?ezzz-C4F9O)3-PhNHMe2 +

[0326] OC(CF3)(C6F5)-OB(zzz / 2ezzz-C4F9O)3-zBu2Al +

[0327] О-С(СРз)(СбР5)-О-В(СбР5О)з-РНзС +

[0328] OC(CF3)(C6F5)-OB(C6F5O)3-PhNHMe2 +

[0329] OC(CF3)(C6F5)-OB(C6F5O)3-Bu2Al +

[0330] О-С(СРз)(СбР5)-О-В(СбР5)з-РНзС +

[0331] OC(CF3)(C6F5)-OB(C6F5)3-PhNHMe2 +

[0332] OC(CF3)(C6F5)-OB(C6F5)3-Bu2Al +

[0333] OC(CF3)(C6F5)-OY(zzz / ?ezzz-C4F9O)3-Ph3C +

[0334] OC(CF3)(C6F5)-OY(zzz / ?ezzz-C4F9O)3-PhNHMe2 + O

[0335]

[0336] -C(CF3)(C6F5)-OY(m / ?em-C4F9O)3-zBu2Al +

[0337] О-С(СРз)(СбР5)-О-¥(СбР5О)з-Р11зС +

[0338] OC(CF3)(C6F5)-OY(C6F5O)3-PhNHMe2 +

[0339] OC(CF3)(C6F5)-OY(C6F5O)3-7BU2A1 +

[0340] О-С(СРз)(СбР5)-О-¥(СбР5)з-Р11зС +

[0341] OC(CF3)(C6F5)-OY(C6F5)3-PhNHMe2 +

[0342] OC(CF3)(C6F5)-OY(C6F5)3-Bu2Al +

[0343] O

[0344]

[0345] -C(CF3)(C6F5)-OY(w3o-C3H7O)(m / ?em-C4F9O)2-Ph3C + OC(CF3)(C6F5)-OY(w3o-C3H7O)(m / ?em-C4F9O)2-PhNHMe2 + OC(CF3)(C6F5)-OY(w3o-C3H7O)(m / 2em-C4F9O)2-zBu2Al + O-CH(C4F9)-O-Al( / zz / ?e / zz-C4F9O)3-Ph3C +

[0346] O-CH(C4F9)-O-Al(zzz / 2ezzz-C4F9O)3'PhNHMe2+

[0347] O-CH(C4F9)-O-Al(zzzz / 2ezzz-C4F9O)3'zBu2Al +

[0348] O-CH(C4F9)-O-Al(C6F5O)3-Ph3C +

[0349] O-CH(C4F9)-O-Al(C6F5O)3-PhNHMe2 +

[0350] O-CH(C4F9)-O-Al(C6F5O)3-Bu2Al +

[0351] O-CH(C4F9)-O-Al(C6F5)3-Ph3C +

[0352] O-CH(C4F9)-O-Al(C6F5)3-PhNHMe2 +

[0353] O-CH(C4F9)-O-Al(C6F5)3-Bu2Al +

[0354] O-CH(C4F9)-O-Al(z / 3o-C3H7O)(zzz / ?ezzz-C4F9O)2-Ph3C +

[0355] O-CH(C4F9)-O-Al(z / 3o-C3H7O)(zzz / 2ezzz-C4F9O)2-PhNHMe2 + O-CH(C4F 9)— O~ Al (изо-Сз H7O)(zzz / ?ezzz-C4F 9O)2~zBu2 Al +

[0356] O-CH(C4F9)-OB(zzzz / ?ezzz-C4F9O)3-Ph3C +

[0357] O-CH(C4F9)-OB(zzz / 2ezzz-C4F9O)3'PhNHMe2 +

[0358] O-CH(C4F9)-OB(zzzz / 2ezzz-C4F9O)3'zBu2Al +

[0359] О-СН(С4р9)-О-В(СбР5О)з-Р11зС +

[0360] O-CH(C4F9)-OB(C6F5O)3-PhNHMe2 +

[0361] O-CH(C4F9)-OB(C6F5O)3-zBu2Al +

[0362] О-СН(С4р9)-О-В(СбР5)з-Р11зС +

[0363] O-CH(C4F9)-OB(C6F5)3-PhNHMe2 +

[0364] O-CH(C4F9)-OB(C6F5)3-zBu2Al +

[0365] O-CH(C4F9)-OY(zzz / ?ezzz-C4F9O)3-Ph3C +

[0366] O-CH(C4F9)-OY(zzz / 2ezzz-C4F9O)3-PhNHMe2 +

[0367] O-CH(C4F9)-OY(zzz / 2ezzz-C4F9O)3'zBu2Al + O-CH(C4F9)-OY(C6F5O)3-Ph3C +

[0368] O-CH(C4F9)-OY(C6F5O)3-PhNHMe2 +

[0369] O-CH(C4F9)-OY(C6F5O)3-Bu2Al +

[0370] O-CH(C4F9)-OY(C6F5)3-Ph3C +

[0371] O-CH(C4F9)-OY(C6F5)3-PhNHMe2 +

[0372] O-CH(C4F9)-OY(C6F5)3-Bu2Al +

[0373] O-CH(C4F9)-OY(w3o-C3H7O)(m / ?em-C4F9O)2-Ph3C +

[0374] O-CH(C4F9)-OY(w3o-C3H7O)(m / 2em-C4F9O)2'PhNHMe2 +

[0375] O-CH(C4F9)-OY(w3o-C3H7O)(m / 2em-C4F9O)2-Bu2Al +

[0376] OC(CF3)2-O-Al(m / ?em-C4F9O)3“Me2Al +

[0377] OC(CF3)2-O-Al(m / ?em-C4F9O)3-[7Bu2Al(PhNMe2)2] +

[0378] OC(CF3)2-O-Al(m / ?em-C4F9O)3-{H[zBu2Al(PhNMe2}2) +

[0379] OC(CF3)2-O-Al(m / ?em-C4F9O)3-(Ci8H37)2NHMe +

[0380] OC(CF3)2-O-Al((4-Me-C6H4)C(CF3)2O)3-Ph3C +

[0381] OC(CF(CF3)2)2-O-Al(m / ?em-C4F9O)3-Ph3C +

[0382] OC(CF3)2-O-Al((CF3)2CHO)3-Ph3C +

[0383] OC(CF3)2-O-Al(O-CF2-CF2-O) 1,5 -Ph3C +

[0384] OC(CF3)2-O-Al(C 10 F7)3-Ph3C +

[0385] OC(CF3)2-O-Al(2-(C6F5)C6F4)3-Ph3C +

[0386] OC(CF3)2-O-Al(3,5-(CF3)2-C6H3)3-Ph3C +

[0387] OC(CF3)2-OB(C 10 F7)3-Ph3C +

[0388] OC(CF3)2-OB(2-(C6F5)C6F4)3-Ph3C +

[0389] OC(CF3)2-OB(3,5-(CF3)2-C6H3)3-Ph3C +

[0390] OC(CF3)2-O-Al(m / ?em-C4F9O)(C6F5O)2-Ph3C +

[0391] OC(CF3)2-O-Al(m / ?em-C4F9O)2(C6F5O)-Ph3C +

[0392] O

[0393]

[0394] -C(CF3)2-O-Ga(m / ?em-C4F9O)3”Ph3C +

[0395] OC(CF3)2-O-Al(m / 2em-C4F9O)2FAl(m / 2em-C4F9O)3“Ph3C +

[0396] OC(CF3)2-O-Al(m / 2em-C4F9O)2(CN)Al(m / 2em-C4F9O)3“Ph3C +

[0397] OC(CF3)2-O-Al(m / 2em-C4F9O)2(OH)Al(m / 2em-C4F9O)2 - Ph3C +

[0398] OC(CF3)2-O-Al(m / 2em-C4F9O)2(CF3COO)Al(m / ?em-C4F9O)3-Ph3C +

[0399] OC(CF3)2-O-Al(m / 2em-C4F9O)2(CF3SO3)Al(m / 2em-C4F9O)3“Ph3C +

[0400] O-C(CP3)2-O-A1(s / 2em-C4p9O)2(imidazolyl)A1(s / 2em-C4p9O)3“Pb3C + It should be noted that in the process of obtaining a solid activating support for the olefin polymerization catalyst of general formula (I), reactions inevitably occur that lead to the formation of compounds of formulas (XIII) and (XIV)

[0401] support-(OC(R 1 )(R 2 )-O)2-ML (XIII)

[0402] support-OC(R 1 )(R 2 )-O-ML-O-support (XIV).

[0403] In the first case, the M atom links two adjacent OC(R) groups bound to the substrate surface. X )(R 2)-O, and in the second, only a portion of the hydroxyl groups on the substrate surface are modified, and the M atom is bound to both the modified and unmodified groups. Since the formation of these compounds is inevitable, solid activating supports containing these groups are also within the scope of the present invention.

[0404] In another aspect, the invention relates to a compound of the general formula (VI): support - O - A' (VI),

[0405] where support is as defined above;

[0406] A' independently represent a functional group of general formula (VII) bound to an oxygen atom of the substrate surface:

[0407] [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y ​​(VII),

[0408] where R 1 , R 2 , M, L, p and y are as defined above;

[0409] Ct' y+is a cation with a charge y, selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, and an R cation 5 mNH4-m + ,

[0410] where R 5 are as defined above,

[0411] w is 0, 1, 2, 3 or 4,

[0412] in this case, any functional groups A' can be linked by covalent bonds to each other.

[0413] In one incarnation Ct' y+ is a cation selected from the group consisting of an alkali metal cation such as lithium, sodium or potassium; and an alkaline earth metal cation such as beryllium, magnesium, calcium, strontium or barium.

[0414] Compounds of general formula (VI) can be used as intermediates in the process for producing a compound of general formula (I).

[0415] In another aspect, the invention relates to a method for preparing a compound of general formula (I) or general formula (VI), comprising the following steps:

[0416] (1) modification of the substrate surface of general formula (VIII):

[0417] support-(OHi- z ) z '(Ct' ' y+ )z / y (VIII), where support, z and y are as defined above;

[0418] Ct' ,у+ represents Ct y+ or Ct' y+ , as defined above;

[0419] by reaction with a carbonyl compound of general formula (IX):

[0420] (R X )(R 2 )C=O (IX),

[0421] where R 1 and R 2 are as defined above;

[0422] with the formation of 1,1-diols derivatives of the general formula (X):

[0423] support-O-[C(R 1 )(R 2 )-OH ( iz)] z '(Ct' ,y+ )z / y (X);

[0424] (2) reacting 1,1-diols of general formula (X) with a compound containing at least one ML bond,

[0425] where M and L are as defined above;

[0426] with the formation of a compound of general formula (I) or (VI).

[0427] In one embodiment, the carbonyl compound of general formula IX is a polyfluorinated ketone.

[0428] In another embodiment, the carbonyl compound of general formula IX is a polyfluorinated aldehyde.

[0429] Preferably, the carbonyl compound of general formula IX is selected from the group consisting of perfluoroacetone, perfluoromethyl ethyl ketone, perfluorodiethyl ketone, perfluoromethyl isopropyl ketone, perfluoroethyl isopropyl ketone, bis(heptafluoroisopropyl) ketone, perfluorocyclohexanone, 1-chloro-1, 1,3,3,3-pentafluoro-2-propanone, 1-bromo-1, 1,3,3,3-pentafluoro-2-propanone, 1-iodo-1, 1,3,3,3-pentafluoro-2-propanone, 1,3-dichloro-1, 1,3,3-tetrafluoro-2-propanone, 1, 1,3,3-tetrafluoro-2-propanone, 1.1.3.3-pentafluoro-2-butanone, 2,2,6,6-tetrafluorocyclohexanone, 2, 3,4, 5,6-pentafluoroacetophenone, perfluoroacetophenone, 2,2,2-trifluoroacetaldehyde, 2, 2, 3,3,3-pentafluoropropanal, 2,2,3,3,4,4,4-heptafluorobutanal, 2, 2, 3,3, 4, 4,5,5-octafluoropentanal, 2,2,3,3,4,4,5,5,5-nonafluoropentanal, 2,2,3,3-tetrafluoropropanal, 2.3.3.3-tetrafluoro-2-(trifluoromethyl)propanal, 2,3,4,4,4-pentafluoro-2-butenal and 2,3,4, 5,6-pentafluorobenzaldehyde.

[0430] Most preferably, the carbonyl compound of formula IX is selected from the group consisting of perfluoroacetone, bis(heptafluoroisopropyl)ketone, perfluoroacetophenone and 2,2,3,3,4,4,5,5,5-nonafluoropentanal.

[0431] Specific examples of compounds containing at least one ML bond are LiAlH4, NaAlH4, Al(C6P5)3, trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, tris(perfluorenyl)alane, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum fluoride, diisobutylaluminum fluoride, diethylaluminum chloride, diisobutylaluminum chloride, diethylaluminum perfluoro- / 77 / 2c / 77-butylate, diisobutylaluminum perfluoro-tert-butylate, diethylaluminum perfluorophenolate, diisobutylaluminum perfluorophenolate, diisobutylaluminum 2,6-di- / i / ?et-butyl-4-methylphenolate, diethylaluminum ethylate, diisobutylaluminum methanesulfonate, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum bis(perfluoro-t / ?e / i-butylate), isobutylaluminum bis(perfluoro-t / ?e / i-butylate), ethylaluminum bis(perfluorophenolate), isobutylaluminum bis(perfluorophenolate), aluminum tris(isopropylate), aluminum tris(phenolate), aluminum tris(acetylacetonate), aluminum tris(perfluorophenolate), aluminum tris(perfluoro-t / ?e / i-butylate,Bis(perfluoro-t / ?e / i-butoxy)aluminum chloride, bis(perfluorophenoxy)aluminum chloride, bis(perfluoro-t / ?et-butoxy)aluminum trifluoromethanesulfonate, bis(perfluoro-t / ?e / i-butoxy)aluminum trifluoroacetate, methylaluminoxane, isobutylaluminoxane, tetraisobutylaluminoxane, hexaisobutylaluminoxane, methylisobutylaluminoxane, LiBH4, NaBH4, B(C6P5)3, BB3, BC13, BBr3, trimethylborate, triisopropylborate, triethylborane, tris(perfluorophenyl)borate, 8C(M(S1Me3)r)3, ¥(M(S1Me3)r)3, La(N(SiMe3)2)3, Nd(N(SiMe3)2)3, Lu(N(SiMe3)2)3, 8с(CH281Mes)3(THF)2, Y(CH2SiMe3)3(THF)2, Lu(CH2SiMe3)3(THF)2, Sc(N(SiHMe2)2)3(THF), Y(N(SiHMe2)2)3(THF)2, La(N(SiHMe2)2)3(THF)2, Nd(N(SiHMe3)2)3(THF)2, Lu(N(SiHMe2)2)3(THF)2, 8с(o-CH2SbH4 Me2)3, ¥(o-CH2SbH4 Me2)3, La(o-CH2SbH4 Me2)3, Nd(o-CH2C6H4NMe2)3, Lu(o-CH2C6H4NMe2)3.,

[0432] Preferably, the compound containing at least one ML bond is LiAlH4, LiBH4, B(C6F3)3, Al(C6F3)3, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum fluoride, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, BF3, BC13, aluminum perfluorophenolate, aluminum perfluoro-tri-butylate, F(o-CH2C6H4NMe2)3.

[0433] Most preferably, the compound containing at least one ML bond is LiAlH4, LiBH4, B(C6F3)3, trimethylaluminum, triisobutylaluminum, diethylaluminum fluoride.

[0434] In one embodiment, at stage 1, the surface of the substrate is modified with the general formula (VIII):

[0435] support-(OHi- z ) z '(Ct' ' y+ )z / y (VIII),

[0436] where z = O, by reaction with a carbonyl compound of general formula (IX), which leads to the formation of 1,1-diols derivatives of general formula (X): support-O

[0437]

[0438] -[C(R 1 )(R 2 )-OH ( iz)] z -(Ct' ,у >y (X),

[0439] where z = 0.

[0440] In another embodiment, in step 1, the surface of a substrate of general formula (VIII), where z = 0, is treated with a base, resulting in the formation of a surface of a substrate of general formula (VIII):

[0441] support-(OHi- z ) z '(Ct' ' y+ )z / y (VIII),

[0442] where z = 1, and y = 1 or 2,

[0443] and then the surface of the substrate of general formula (VIII), where z = 1 and y = 1 or 2, is modified with a carbonyl compound of general formula (IX), which leads to the formation of 1,1-diols derivatives of general formula (X):

[0444] support-O-[C(R 1 )(R 2 )-OH(iz)] z '(Ct” y+ )z / y ,

[0445] where z = 1, and y = 1 or 2.

[0446] In one embodiment, the treatment of the surface of a substrate of general formula (VIII), where z = 0, with a base is carried out in a solvent medium with stirring at a temperature of -80 to 100°C. Preferably, the solvent is selected from the group consisting of benzene, toluene, hexane, heptane, diethyl ether, and tetrahydrofuran.

[0447] Preferably, the base is selected from the group consisting of hydrocarbyllithium, dihydrocarbylmagnesium, hydrocarbylmagnesium halide, lithium hexamethyldisilazide, sodium hexamethyldisilazide, lithium dihydrocarbylamide, and trihydrocarbylamine. Most preferably, the base is selected from n-butyllithium, dibutylmagnesium, n-butylmagnesium chloride, and (C|xH37)2XMe.

[0448] In one embodiment, y = 1, and the cation is Ct” y+ is a singly charged cation Ct” + .

[0449] Preferably the cation Ct” +selected from the group consisting of alkali metal cations, tetrahydrocarbylammonium, trihydrocarbylammonium, dihydrocarbylammonium, or monohydrocarbylammonium. Most preferably, the Ct cation" + selected from Li cations + , Na + , TO + , (CisH37)2NHMe + .

[0450] In another embodiment, y = 2, and the cation is Ct” y+ is a divalent cation Ct” 2+ .

[0451] Preferably the cation Ct” 2+ selected from alkaline earth metal cations. The most preferred cation is Ct” 2+ is a Mg cation 2+ In one embodiment, at stage 1, the modification of the surface of the substrate of general formula (VIII) by reaction with a carbonyl compound of general formula (IX) is carried out at a temperature from -80 to 100°C.

[0452] In one embodiment, in step 1, the modification of the surface of the substrate of general formula (VIII) by reaction with a gaseous carbonyl compound of general formula (IX) is carried out without a solvent in an atmosphere of the carbonyl compound with stirring.

[0453] In one embodiment, in step 1, the modification of the surface of the substrate of general formula (VIII) by reaction with a liquid carbonyl compound of general formula (IX) is carried out without a solvent in a liquid carbonyl compound medium with stirring.

[0454] In another embodiment, in step 1, the modification of the surface of the substrate of general formula (VIII) by reaction with a carbonyl compound of general formula (IX) is carried out in a solvent medium with stirring. Preferably, the solvent is selected from the group consisting of benzene, toluene, hexane, heptane, diethyl ether, and dichloromethane.

[0455] Preferably, in step 1, the modification of the silica gel surface by reaction with perfluoroacetone is carried out without a solvent in an atmosphere of gaseous perfluoroacetone at room temperature.

[0456] Preferably, in step 1, the modification of the silica gel surface by reaction with perfluoroacetophenone or bis(heptafluoroisopropyl)ketone is carried out in a toluene medium at room temperature.

[0457] Preferably, in step 1, the modification of the silica gel surface by reaction with nonafluoropentanal is carried out without a solvent in a liquid nonafluoropentanal medium at room temperature.

[0458] In one embodiment, in step 2, the 1,1-diols derivatives of general formula (X)

[0459] support-O

[0460]

[0461] -[C(R 1 )(R 2 )-OH ( iz)] z '(Ct' ,у >y (X);

[0462] are brought into interaction with a compound containing at least one ML bond,

[0463] where M and L are as defined above;

[0464] to form a compound of general formula (I). In another embodiment, in step 2, the 1,1-diols derivatives of general formula (X), where z = 0, are reacted with a compound containing at least one ML bond,

[0465] where M and L are as defined above;

[0466] to form a compound of general formula (I).

[0467] In another embodiment, in step 2, the 1,1-diols derivatives of general formula (X), where z = 1 and y = 1 or 2, are reacted with a compound containing at least one ML bond,

[0468] where M and L are as defined above;

[0469] to form a compound of general formula (I).

[0470] In another embodiment, in step 2, the 1,1-diols derivatives of general formula (X), where z = 0, are treated with a base, which leads to the formation of 1,1-diols derivatives of general formula (X), where z = 1 and y = 1 or 2, and then the 1,1-diols derivatives of general formula (X), where z = 1 and y = 1 or 2, are reacted with a compound containing at least one ML bond,

[0471] where M and L are as defined above;

[0472] to form a compound of general formula (I).

[0473] In one embodiment, the treatment of 1,1-diol derivatives of general formula (X), where z = 0, with a base is carried out in a solvent medium with stirring at a temperature of -80 to 100°C. Preferably, the solvent is selected from the group consisting of benzene, toluene, hexane, heptane, diethyl ether, tetrahydrofuran, dichloromethane, ethyl acetate, methanol, ethanol, isopropanol, and acetonitrile.

[0474] Preferably, the base is selected from the group consisting of hydrocarbyllithium, dihydrocarbylmagnesium, hydrocarbylmagnesium halide, lithium hexamethyldisilazide, sodium hexamethyldisilazide, lithium dihydrocarbylamide, lithium alkoxide, sodium alkoxide, potassium alkoxide, and trihydrocarbylamine. Most preferably, the base is selected from n-butyllithium, dibutylmagnesium, n-butylmagnesium chloride, (CisH37)2NMe, and PdNMe.

[0475] In one embodiment, y = 1, and the cation is Ct” y+ is a singly charged cation Ct” + .

[0476] Preferably the cation Ct” + selected from the group consisting of alkali metal cations, tetrahydrocarbylammonium, trihydrocarbylammonium, dihydrocarbylammonium, and monohydrocarbylammonium. The most preferred cation is Ct" + selected from Li cations + , Na + , TO + , (CisH37)2NHMe + , PhNHMe2 + .

[0477] In another embodiment, y = 2, and the cation is Ct”y+ is a divalent cation Ct” 2+ .

[0478] Preferably the cation Ct” 2+ selected from the group consisting of alkaline earth metal cations. The most preferred cation is Ct” 2+ is a Mg cation 2+ .

[0479] In one embodiment, in step 2, the reaction of 1,1-diols derivatives of general formula (X) with a compound containing at least one ML bond is carried out in a solvent medium at a temperature of -30 to 110°C and stirring.

[0480] Preferably, the solvent is selected from the group consisting of hexane, heptane, octane, benzene, toluene, diethyl ether and tetrahydrofuran.

[0481] Preferably, the reaction of 1, 1-diols derivatives of the general formula (X), where support = silica gel, az = 0, and Li AIH4 is carried out in diethyl ether at room temperature.

[0482] Preferably, the reaction of 1, 1-diols derivatives of the general formula (X), where support = silica gel, az = 0, m and LiBH4 is carried out in a mixture of diethyl ether and tetrahydrofuran at room temperature.

[0483] Preferably, the reaction of 1,1-diols derivatives of the general formula (X), where support = silica gel, az = 0, and diethylaluminum fluoride is carried out in toluene at room temperature.

[0484] Preferably, the reaction of 1,1-diols derivatives of the general formula (X), where support = silica gel, az = 0, and Al(0 / Pr)3 is carried out in toluene at 100°C.

[0485] Preferably, the reaction of 1,1-diols derivatives of the general formula (X), where support = silica gel, az = 0, and trimethylaluminum is carried out in toluene at 0°C.

[0486] Preferably, the reaction of 1, 1-diols derivatives of the general formula (X), where support = silica gel, az = 0, and methylaluminoxane is carried out in toluene in the temperature range from -40 to -30°C.

[0487] Preferably, the treatment of 1,1-diols derivatives of the general formula (X), where support = silica gel, az = 0, with butyl lithium as a base is carried out in hexane at -80°C, and then the resulting 1,1-diols derivatives of the general formula (X), where support = silica gel, z = 0, y = 1, and Ct” are reacted y+ = Li + , with B(C6P3)3 in a diethyl ether-toluene mixture at -80°CB, in one embodiment, step 2 comprises a substitution reaction in a functional group of general formula (II) or (VII) of a compound of general formula (I) or (VI), respectively, of at least one ligand L in the coordination sphere of an atom M with at least one ligand X, where M, L and X are as defined above, provided that X is different from L.

[0488] In one embodiment, the substitution reaction in a functional group of general formula (II) or (VII) of a compound of general formula (I) or (VI), respectively, of at least one ligand L in the coordination sphere of an atom M with at least one ligand X is carried out in a solvent medium at a temperature of -80 to 100°C and with stirring. Preferably, the solvent is selected from the group consisting of benzene, toluene, hexane, heptane, diethyl ether, tetrahydrofuran, and dichloromethane.

[0489] In a specific embodiment, the functional group of general formula (VII),

[0490] [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y,

[0491] where R 1 = R 2 = CF3, L = H, n = 3, y = 1, a Ct' y+ =Li + ,

[0492] are reacted with perfluoro-t / zet-butanol in a toluene medium at 20-30°C and stirring, which results in the substitution of at least one ligand L by at least one ligand X, where X = perfluoro-t / zet-butoxy.

[0493] In another specific embodiment, the functional group of general formula (VII),

[0494] [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y,

[0495] where R 1 = R 2 = CF3, L = H, n = 3, y = 1, a Ct' y+ = Li + ,

[0496] are reacted with 1,1,1,3,3,3-hexafluoropropan-2-ol in a toluene medium at 20-30°C and stirring, which results in the substitution of at least one ligand L by at least one ligand X, where X = 1, 1,1, 3,3,3-hexafluoropropan-2-oxy.

[0497] In another specific embodiment, the functional group of general formula (VII),

[0498] [C(R 1 )(R 2 )-O-MLn] '(Ct'y+ )i / y,

[0499] where R 1 = R 2 = CF3, L = H, n = 3, y = 1, a Ct' y+ = Li + ,

[0500] are reacted with perfluorophenol in a toluene medium at 20-30°C and stirring, which results in the substitution of at least one ligand L with at least one ligand X, where X = perfluorophenoxy. In another specific embodiment, the functional group of general formula (VII),

[0501] [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y ,

[0502] where R 1 = C6F5, R 2 = CF3, L = H, n = 3, y = 1, a Ct' y+ = Li + ,

[0503] are reacted with perfluoro-t / zet-butanol in a toluene medium at 20-30°C and stirring, which results in the substitution of at least one ligand L by at least one ligand X, where X = perfluoro-t / zet-butoxy.

[0504] In another specific embodiment, the functional group of general formula (VII),

[0505] [C(R 1 )(R 2 )-O-MLn] '(Ct' y+ )i / y,

[0506] where R 1 = C4F9, R 2 = N, L = N, n = 3, y = 1, a Ct' y+ = Li + ,

[0507] are reacted with perfluoro-t / zet-butanol in a toluene medium at 20-30°C and stirring, which results in the substitution of at least one ligand L by at least one ligand X, where X = perfluoro-t / zet-butoxy.

[0508] In another specific embodiment, the functional group of general formula (VII),

[0509] [C(R 1 )(R 2 )-O-MLn] '(Ct' y+ )i / y,

[0510] where R 1 = R 2 = Z-C3F7, L = H, n = 3, y = 1, a Ct' y+ = Li + ,

[0511] are reacted with perfluoro-t / zet-butanol in a toluene medium at 20-30°C and stirring, which results in the substitution of at least one ligand L by at least one ligand X, where X = perfluoro-t / zet-butoxy.

[0512] In another specific embodiment, the functional group of general formula (II),

[0513] [C(R 1 )(R 2 )-O-MLn] z '(Ct' y+ )z / y ,

[0514] where R 1 = R 2 = CF3, L = zBu, n = 2, z = 0,

[0515] are reacted with perfluoro-3-butanol in a toluene medium at 20-30°C and stirring, which leads to the replacement of at least one ligand L with at least one ligand X, where X = perfluoro-3-butoxy.

[0516] In one embodiment, the method further comprises a substitution reaction of the cation Ct' y+ in a compound of general formula (VI), (VIII) or (X) per cation Ct y+ , where Ct y+ and Ct'y+ , are as defined above.

[0517] In one of the incarnations of Ct y+ is a cation capable of converting a neutral transition metal complex into a cationic complex capable of catalyzing the polymerization of olefins, with a charge y, where y is 1 or 2. In particular, Ct y+ selected from the group consisting of R 4 3C + , R 5 3NH + , R 6 2Al + , ((R 5 3N)2AlR 6 2) + and H(R 5 3N-AlR 6 2)2 + , where R 4 , R 5 , R 6 are as defined above.

[0518] Preferably, Ct y+ selected from the group consisting of triphenylmethyl, N,N-dimethylanilinium, methyldi(octadecyl)ammonium, methyl(octadecyl)(hexadecyl)ammonium, methyldi(hexadecyl)ammonium and methyldi(tetradecyl)ammonium, ((PhNMe2)2AlBu2) + , H(PhNMe2-AlzBu2)2 + .

[0519] Most preferably, Ct y+ selected from the group consisting of triphenylmethylium, N,N-dimethylanilinium, Bu2Al + , ((PhNMe2)2AlBu2) + , H(PhNMe2-AlBu2)2 + .

[0520] In one embodiment, the substitution reaction of the cation Ct' y+ in a compound of general formula (VI), (VIII) or (X) per cation Ct y+ The reaction is carried out in a solvent environment at a temperature of -80 to 100°C and with stirring. Preferably, the solvent is selected from the group consisting of benzene, toluene, hexane, heptane, diethyl ether, tetrahydrofuran, and dichloromethane.

[0521] In a specific embodiment, the functional group of general formula (VII),

[0522] [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y ​​(II)

[0523] where R 1 = R 2 = CF3, M = Al, L = (Z-C4F9O), n = 3, y = 1, a Ct' y+ = Li +

[0524] interact with PhNHMe2 +Cl" in a dichloromethane medium at 20-30°C and stirring, which leads to the replacement of the Ct' cation y+ per cation Ct + , where Ct + = PhNHMe2 + .

[0525] In another specific embodiment, the functional group of general formula (VII),

[0526] [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y ​​(II)

[0527] where R 1 = R 2 = CF3, M = Al, L = (Z-C4F9O), n = 3, y = 1, a Ct' y+ = Li +

[0528] are brought into interaction with Pd3CC1 in a toluene medium at 20-30°C and stirring, which leads to the substitution of the Ct' cation y+ per cation Ct + , where Ct + = РйзС + .

[0529] In another specific embodiment, the functional group of general formula (VII),

[0530] [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y ​​(II)

[0531] where R 1 = R 2= CF3, M = Al, L = (Z-C4F9O), n = 3, y = 1, a Ct' y+ = Li + sequentially treated at 20-30°C and stirring PhNHMe2 + Cl" in a dichloromethane medium, and then AlBu3 in a toluene medium, which leads to the substitution of the Ct' cation y+ per cation Ct + , where Ct + = [ / Bu2Al(PhNMe2)2] + .

[0532] In another specific embodiment, the functional group of general formula (VII),

[0533] [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y (II)

[0534] where R 1 = R 2 = CF3, M = Al, L = ( / -C4F9O), n = 3, y = 1, a Ct' y+ = Li + sequentially treated at 20-30°C and stirring PhNHMe2 + Cl" in a dichloromethane medium, then AlBu3 in a toluene medium, and then / Bu3AlH in a toluene medium, which leads to the substitution of the Ct' cation y+ per cation Ct + , where Ct + = {H[ / Bu2Al(PhNMe2)2]} + .

[0535] According to another aspect, the invention relates to the use of a compound of general formula (I) as a solid activating support for an olefin polymerization catalyst.

[0536] According to another aspect, the invention relates to an olefin polymerization catalyst formed by the reaction of a compound of general formula (I) described above and a precatalyst containing a neutral or cationic transition metal complex.

[0537] In one embodiment, said olefin polymerization catalyst is a compound of general formula (XI)

[0538] support-O-[C(R 1 )(R 2 )-OML n ]' Т M + (XI),

[0539] where support, R 1 , R 2 , M, L and n are as defined above,

[0540] Т M +is a transition metal complex containing at least one hydrocarbyl group bound to a transition metal atom and a vacant coordination site that can be reversibly occupied by a dissociable ligand.

[0541] In another incarnation of the complex Т M + is a complex of titanium, zirconium or hafnium.

[0542] In another incarnation of the complex Т M + contains at least one ligand selected from the group consisting of a substituted or unsubstituted cyclopentadienyl ligand, a chelate ligand, a monodentate ligand bonded to a metal atom via a nitrogen or oxygen atom.

[0543] In specific examples of the implementation of the complex Т M +selected from the group consisting of (n-BuC₅H₄)₂ZrMe₂, rac-Me₂Si(2-Me-4-Ph-inden-1-yl)₂ZrMe₂, Me2Si(C5Me4)N(m / 2em-Bu)TiMe2, 6",6""""-(propane-1,3-diylbis(oxy))bis(3,3",5-tri-t / ?et-butyl-5'-methyl-[1,G:3',1"-terphenyl]-2'-oxy) dimethylzirconium, 6",6 -(propane-1,3-diylbis(oxy))bis(3,3",5-tri-t / ?et-butyl-5'-methyl-[1,G:3',1"-terphenyl]-2'-oxy) dimethylhafnium.

[0544] According to another aspect, the invention relates to a catalyst composition comprising the olefin polymerization catalyst described above and an organoaluminum compound. Preferably, said organoaluminum compound is an organoaluminum compound capable of acting as a catalyst poison neutralizer.

[0545] In one embodiment, the organoaluminum compound is represented by the general formula (XII):

[0546] AlR 9 n OR 10 3-n (XII),

[0547] where R 9 and R 10independently selected from the group consisting of alkyl, cycloalkyl, aryl substituted with one or more hydrocarbyl groups, and a hydrogen atom,

[0548] and n is 1, 2, or 3.

[0549] In one embodiment, at least one of R 10 in formula (XII) is 2,6-di-t / ?et-alkylphenyl, optionally substituted with one or more substituents independently selected from the group consisting of hydrocarbyloxy group, dihydrocarbylamino group, alkyl, cycloalkyl and aryl, substituted with one or more hydrocarbyl groups.

[0550] In particular, said organoaluminum compound is a compound selected from the group consisting of the following compounds: trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, dimethylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate, diethylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate, diisobutylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate, methylaluminum bis(2,6-di-t / zet-butyl-4-methylphenolate), ethylaluminum bis(2,6-di-t / ?et-butyl-4-methylphenolate), isobutylaluminum bis(2,6-di-t / ?et-butyl-4-methylphenolate), methylaluminoxane, isobutylaluminoxane, tetraisobutylaluminoxane, hexaisobutylaluminoxane, methylisobutylaluminoxane.

[0551] According to another aspect, the invention relates to a method for producing the above-described olefin polymerization catalyst or the above-described catalytic composition, comprising reacting a compound of general formula (I) with a precatalyst containing a neutral or cationic transition metal complex.

[0552] In one embodiment, said method comprises reacting a compound of general formula (I), in which the functional group A is a functional group of general formula (III), with a precatalyst containing a cationic transition metal complex.

[0553] In another embodiment, said method comprises reacting a compound of general formula (I), in which the functional group A is a functional group of general formula (IV), with a precatalyst containing a neutral transition metal complex.

[0554] In one embodiment, a compound of general formula (I) is reacted with a precatalyst containing a neutral or cationic transition metal complex in an organic solvent. Preferably, the solvent is selected from the group consisting of diethyl ether, dichloromethane, pentane, hexane, heptane, octane, benzene, and toluene. Most preferably, the solvent is selected from the group consisting of hexane and toluene.

[0555] In another embodiment, the compound of general formula (I) is reacted with a precatalyst containing a neutral or cationic transition metal complex in the presence of an olefin. The olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, or vinylcyclohexane.

[0556] In another embodiment, the compound of general formula (I) is reacted with a precatalyst containing a neutral or cationic transition metal complex at a temperature of from -30 to 300°C.

[0557] In another embodiment, a compound of general formula (I) is reacted with a precatalyst containing a neutral or cationic transition metal complex in the presence of a compound capable of acting as a catalyst poison neutralizer. Preferably, the compound capable of acting as a catalyst poison neutralizer is an organoaluminum compound of general formula (XII).

[0558] In another aspect, the invention relates to a method for polymerizing olefins, comprising reacting the above-described catalyst or the above-described catalyst composition with at least one olefin. In one embodiment, the method comprises reacting the catalyst or catalyst composition with one olefin. In another embodiment, the method comprises reacting the catalyst or catalyst composition with at least two olefins. In another embodiment, the olefins are alpha-olefins. Preferably, the olefins contain from 2 to 40 carbon atoms, more preferably from 3 to 20 carbon atoms. In particular, the olefins can be selected from ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, or vinylcyclohexane.

[0559] In another embodiment, one of the olefins is ethylene and the second olefin is an alpha-olefin containing from 3 to 20 carbon atoms. In particular, one of the olefins is ethylene and the second olefin is propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, or vinylcyclohexane.

[0560] In one embodiment, the method further comprises a prepolymerization step in which the catalyst or catalyst composition is reacted with at least one olefin at a lower olefin concentration and / or temperature compared to the concentration and temperature of the olefin polymerization step. In one embodiment, the prepolymerization step comprises reacting the catalyst or catalyst composition with an alpha-olefin containing from 3 to 20 carbon atoms. In particular, the alpha-olefin in the prepolymerization step is 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, or vinylcyclohexane.

[0561] The olefin (co)polymerization process can be carried out according to known techniques, for example, by suspension polymerization using an inert hydrocarbon diluent or by bulk polymerization using a liquid monomer (e.g., propylene) as the reaction medium. Furthermore, the (co)polymerization process can be carried out in the gas phase using a fluidized bed reactor or a mechanically stirred bed reactor.

[0562] Typically, (co)polymerization conditions include a temperature of 20 to 120°C, preferably 40 to 80°C. In gas-phase (co)polymerization, the operating pressure is typically 0.5 to 10 MPa, preferably 1 to 5 MPa. In bulk (co)polymerization, the operating pressure is typically 1 to 6 MPa, preferably 1.5 to 4 MPa. Hydrogen or other compounds capable of acting as chain transfer agents can be used to control the molecular weight of the polymer.

[0563] EXAMPLES

[0564] Examples C1 - C22 and comparison examples CC1 - CC3: examples of obtaining activating carriers

[0565] General information

[0566] The synthesis of activating carriers at all stages was carried out in an inert gas atmosphere (argon).

[0567] Hexane, toluene, and dichloromethane were degassed by bubbling with dry argon and dried over 4 A molecular sieves. Diethyl ether and THF were distilled over sodium in the presence of benzophenone ketyl.

[0568] The residual water content was determined by Fischer titration on a Mettler Toledo C20 automatic titrator.

[0569] Solid substrate made of inorganic oxide SiO2-ES70 600 denotes silica gel grade ES70, calcined at 600°C for 12 hours, with a surface OH group concentration of 0.6 mmol / g or 0.8 mmol / g.

[0570] Solid substrate made of inorganic oxide SiO2-ES70 800denotes silica gel grade ES70, calcined at 800°C for, with a concentration of surface silanol groups of 0.6 mmol / g.

[0571] The solid substrate made of inorganic oxide SiO2-Al2O3Cariact P10 is a mixed silicon-aluminum oxide of the Cariact P10 brand with an aluminum mass fraction of 4.7%, dried in a vacuum for 6 hours at 200°C.

[0572] The solid substrate made of inorganic oxide SiO2-Sylopol952 is silica gel of the Sylopol 952 brand dried in a vacuum for 6 hours at 200°C.

[0573] The solid support of inorganic oxide Al2O3 is aluminum oxide according to Brockmann I, neutral, dried in vacuum for 6 hours at a temperature of 200°C.

[0574] To obtain quantitative NMR spectra, the following technique was used. The powder to be studied was placed in an ampoule and then pumped down a vacuum line to a pressure of 1 x 10 -6Torr. The ampoule was sealed from the atmosphere and transferred to a zirconium rotor in a dry box. Nuclear NMR spectra 1 H, 13 C, 19 F, 27 Al and 29 Magic angle spin (MAS) spectra of a solid sample were recorded on a BRUKER AVANCE-II 400 WB spectrometer at frequencies of 400.13( 1 H), 100.13 ( 13 C), 376.45 ( 19 F), 104.3 ( 27 Al) and 79.5 ( 29 Si) MHz using a 4 mm H / F / X MAS WVT probe (sample rotation speed – 10 ( 1 H, 13 C, 19 F, 29 Si) and 12 ( 27 Al) kHz). A 1-pulse technique with 90° was used ( 1 H, 13 C, 27 Al, 29 Si) and 2-pulse Han-echo technique π / 2 – τ – π – τ ( 19 F), where τ is proportional to n = 1 rotor revolution. Chemical shifts (3) are given in parts per million relative to an external standard. SiMe4( 1 H, 13C, 29 Si), 1M solutions of NH4F ( 19 F) and Al(NO3)3( 27 Al).

[0575] The following technique was used to obtain IR spectra (DRIFT). In a glovebox with an argon atmosphere, a weighed portion of the test sample (35 mg) was mixed with dry KBr (665 mg, Acros, IR-grade). The resulting mixture in an amount of 700 mg was thoroughly mixed with a spatula and ground in an agate mortar. An aliquot of the resulting powder was taken and analyzed by Fourier transform infrared spectroscopy on an Agilent Cary 630 FTIR instrument equipped with a DRIFT diffuse reflectance attachment. Acquisition parameters: 64 background scans, 512 sample scans, gain of 216, Happ-Haenszel apodization, acquisition window of 650-4000 cm -1 , resolution 4 cm -1 ; the Kubelka-Munk transformation was applied to the obtained PC spectra.

[0576] Example C1

[0577] (SiO2-ES70 600 )-OC(CF3)2-O-Al(»2pem-C4F9O)3-Ph3C +

[0578] (SiO2-ES70 600 )-OC(CF3)2-OH

[0579] 4.50 g silica gel SiO2-ES70 600 (0.8 mmol / g) was placed in a Schlenk flask, the argon atmosphere was replaced with an atmosphere of perfluoroacetone, the silica gel was kept under a constant pressure (1 atm) of perfluoroacetone for 4 hours at room temperature, and then kept in a vacuum for 2 hours at 50 ° C. Yield 4.43 g of white powder. DRIFT (cm -1 ): 3602 (C-OH), 724 (CF). 'H MAS NMR (400 MHz, 10 kHz): 3.5 (=Si-OC(CF3)2-OJ7). 19 F MAS NMR (376 MHz, 10 kHz): δ -84.4 (≡Si-OC(CF3)2-OH). 29 Si MAS NMR (79 MHz, 10 kHz): δ -108.3 (≡-OC(CF3)2-OH).

[0580] (SiO2-ES70 600 )-OC(CF3)2-O-AlH3-Li3.00 g (SiO2-ES70 600)-OC(CF3)2-OH was suspended in 120 ml of dry diethyl ether and a solution of freshly recrystallized lithium aluminum hydride (273 mg, 7.20 mmol) in 20 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 hours, after which the precipitate was separated by filtration on a sintered glass filter and washed with 3 x 10 ml of diethyl ether, and then dried in vacuo for 3 h at 50 °C and used entirely in the next step. DRIFT (cm -1 ): 2984 (alkyl, Al→Et2O), 2943 (alkyl, Al→Et2O), 2897 (alkyl, Al→Et2O), 1860 (Al-H), 724 (CF), 689 (CF). 1 H MAS NMR (400 MHz, 10 kHz): δ 3.7, 1.1 (Et2O). 19 F MAS NMR (376 MHz, 10 kHz): δ -76.7 (≡Si-OC(CF3)2-OAlH3 - ). 27 Al MAS NMR (104 MHz, 10 kHz): δ 54.4 ((≡Si-OC(CF3)2-O)2H2), 39.5 (≡Si-OC(CF3)2-OH3 - ).

[0581] (SiO2-ES70 600 )-OC(CF3)2-O-Al(m / ?em-C4F9O)3-Li +

[0582] (SiO2-ES70 600 )-OC(CF3)2-O-AlH3- Li + , obtained in the previous step, was suspended in 50 ml of toluene and 2.01 ml (14.4 mmol) of perfluoro-(7?) / 2c / 77-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 h at 50°C and used entirely in the next step. DRIFT (cm -1 ): 1299, 1250, 977 (C-), 728 (C-). 1 H MAS NMR (400 MHz, 10 kHz): δ 4.6 (residual protons). 19 F MAS NMR (376 MHz, 10 kHz): 3 -73.8 (=81-O-C(CPz)2-OA1(t / ?et-C4A)z“), -75.7 (=Si-OC(CFj)2-OAl(m / 2em-C4F9O)3“). 27 Al MAS NMR (104 MHz, 10 kHz): 339.6 (=81-O-C(SR3)2-OL / (t / 2et-C4p9O)z' )•

[0583] (SiO2-ES70 600 )-OC(CF3)2-O-Al(m / ?em-C4F9O)3-Ph3C +

[0584] (SiO2-ES70 600 )-OC(CF3)2-O-Al(m / 2em-C4F9O)3“Li +, obtained in the previous step, was suspended in 50 ml of toluene and 2.00 g (7.2 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 3.10 g of activating carrier as an orange powder. DRIFT (cm -1 ): 1584 (Ph3C + ), 1484 (Ph3C + ), 1453 (Ph3C + ), 1360 (Ph3C + ), 1296, 976 (C-), 728 (C-), 704 (C-), 688 (CF). 1 H MAS NMR (400 MHz, 10 kHz): δ 8.0 (3C + ), 7.6 (3C + ), 7.4 (3C + ), 6.7 (3C + ). 13 C MAS NMR (100 MHz, 10 kHz): δ 141.9 (3C + ),130.3 (Radar + ), 124.2- 118.7 ((PfeC + ) + (=Si-O-C(CP3)2-OA1(C(CP3)3)3-), 81.1 (=Si-O-C(CP3)2-OA1(C(CP3)3)3“), 79.2

[0585]

[0586] (≡Si-OC(CF3)2-OAl(-C4F9O)3 - ). 19 F MAS NMR (376 MHz, 10 kHz) 27 Al MAS NMR (104 MHz, 10 kHz): 3 49.7 (=Si-OC(CF3)2-OH / -(s / ?et-C4p9O)3). ICP-OES (wt.%): Al - 1.30.

[0587] Example C2

[0588] (A12O3)-O-C(CP3)2-O-A1(w / >esh-C4P9O)3-PbzS +

[0589] (A12O3)-O-C(CP3)2-OH

[0590] 4.00 g of aluminum oxide were placed in a Schlenk flask, the argon atmosphere was replaced with an atmosphere of perfluoroacetone, the silica gel was kept under a constant pressure (1 atm) of perfluoroacetone for 4 hours, and then kept in a vacuum for 2 hours at 50°C. Yield 4.13 g of white powder.

[0591] (A12Oz)-O-S(SRz)2-O-A1Нз“1л +

[0592] 3.00 g of (Al2O3)-O-C(CP3)2-OH were suspended in 120 ml of dry diethyl ether and a solution of freshly recrystallized lithium aluminum hydride (273 mg, 7.20 mmol) in 20 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of diethyl ether and dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0593] (Al2O3)-OC(CF3)2-O-Al(-C4F9O)3-Li +

[0594] (A12Oz)-O-C(SRz)2-O-A1Нз“ы + The product obtained in the previous step was suspended in 50 ml of toluene and 2.01 ml (14.4 mmol) of perfluoro-(7?) / 9c / 77-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene and dried in vacuum for 3 h at 50°C.

[0595] (Al2O3)-OC(CF3)2-O-Al(-C4F9O)3-Ph3C +

[0596] (A12Oz)-O-C(SRz)2-O-A1(t / ?et-C4p9O)z“Y + suspended in 50 ml of toluene and 2.00 g (7.20 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 2 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml with hexane and dried in vacuum for 3 h at 50°C. Yield 2.17 g of activating carrier as an orange powder. DRIFT (cm' 1 ): 1584 (Ph3C + ), 1483 (Ph3C + ), 1451 (Ph3C + ), 1358 (Ph3C + ), 1296, 963 (CF), 724 (CF).

[0597] Example C3

[0598] (SiO2-Al2O3Cariact Pl 0)-O-C(CP3)2-O-A1(w / >esh-C4P9O)3-PbzC +

[0599] (SiCh-AhCh Cariact Pl 0)-OC(CF3)2-OH

[0600] 4.50 g of mixed silicon-aluminum oxide SiO2-Al2O3Cariact P10 were placed in a Schlenk flask, the argon atmosphere was replaced with an atmosphere of perfluoroacetone, the mixed silicon-aluminum oxide was kept under a constant pressure (1 atm) of perfluoroacetone for 4 hours, and then kept in a vacuum for 2 hours at 50°C. Yield 4.43 g of white powder.

[0601] (SiCh-AhCh Cariact Pl 0)-0-C(CF3)2-0-A1H3-Li +

[0602] 3.00 g of (SiCh-AhCh Cariact P10)-OC(CF3)2-OH were suspended in 120 ml of dry diethyl ether, and a solution of freshly recrystallized lithium aluminum hydride (273 mg, 7.20 mmol) in 20 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of diethyl ether, dried in vacuo for 3 h at 50°C, and used entirely in the next step.

[0603] (SiCh-AhCh Cariact P10)-0-C(CF3)2-0-Al(m / ?em-C4F90)3“Li+

[0604] (SiCh-AhCh Cariact P10)-OC(CF3)2-O-AlH3“Li + The product obtained in the previous step was suspended in 50 ml of toluene, and 2.01 ml (14.4 mmol) of perfluoro-t / z-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 h at 50°C, and used entirely in the next step.

[0605] (SiCh-AhCh Cariact P

[0606]

[0607] 10)-OC(CF3)2-O-Al(m / ?em-C4F9O)3-Ph3C(SiCh-AhCh Cariact Р10)-0-С(СРз)2-0-А1(т / ?ет-С4р90)з“1л +, obtained in the previous step, was suspended in 50 ml of toluene and 2.00 g (7.20 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 3.10 g of activating carrier as an orange powder. DRIFT (cm' 1 ): 1584 (RijsS + ), 1483 (RijsS + ), 1451 (RijsS + ), 1360 (RijsS + ), 1297, 974 (CF), 730 (CF), 702 (CF), 688 (CF).

[0608] Example C4

[0609] (SiO2-Sy1oro1952)-0-C(CP3)2-0-A1(w / >esh-C4P90)3-PbzS +

[0610] (SiO2-Sylopol952)-OC(CF3)2-OH

[0611] 4.50 g of SiCh-Sylopol 952 silica gel were placed in a Schlenk flask, the argon atmosphere was replaced with an atmosphere of perfluoroacetone, the silica gel was kept under a constant pressure (1 atm) of perfluoroacetone for 4 hours, and then kept in a vacuum for 2 hours at 50°C. Yield 4.38 g of white powder.

[0612] (SiO2-Sylopol952)-OC(CF3)2-O-AlH3-Li +

[0613] 3.00 g of (SiO2-Sylopol952)-OC(CF3)2-OH (2.40 mmol) were suspended in 120 ml of dry diethyl ether and a solution of freshly recrystallized lithium aluminum hydride (273 mg, 7.20 mmol) in 20 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of diethyl ether, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0614] (SiO2-Sylopol952)-OC(CF3)2-O-Al(m / ?em-C4F9O)3“Li +

[0615] (SiO2-Sylopol952)-OC(CF3)2-O-AlH3~Li + , obtained in the previous step, was suspended in 50 ml of toluene and 2.01 ml (14.4 mmol) of perfluoro-t / et-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 h at 50°C and used entirely in the next step. (SiO2-Sylopol952)-OC(CF3)2-O-Al(m / ?em-C4F9O)3-Ph3C +

[0616] (SiO2-Sylopol952)-OC(CF3)2-O-Al(m / ?em-C4F9O)3“Li +, obtained in the previous step, was suspended in 50 ml of toluene and 2.00 g (7.20 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 3.10 g of activating carrier as an orange powder. DRIFT (cm' 1 ): 1584 (Ph3C + ), 1485 (Ph3C + ), 1454 (Ph3C + ), 1358 (Ph3C + ), 1296, 976 (CF), 727 (CF), 704 (CF), 689 (CF).

[0617] Example C5

[0618] (SiO2-ES70 800 )-OC(CF3)2-O-Al(»2pem-C4F9O)3-Ph3C +

[0619] (SiO2-ES70 800 )-OC(CF3)2-OH

[0620] 5.85 g silica gel SiO2-ES70 800(0.6 mmol / g) was placed in a Schlenk flask, the argon atmosphere was replaced with an atmosphere of perfluoroacetone, the silica gel was kept under a constant pressure (1 atm) of perfluoroacetone for 4 h, and then kept in a vacuum for 2 h at 50°C and completely used in the next step.

[0621] (SiO2-ES70 800 )-OC(CF3)2-O-AlH3-Li +

[0622] (SiO2-ES70 800 )-OC(CF3)2-OH obtained in the previous step was suspended in 150 ml of dry diethyl ether and a solution of freshly recrystallized lithium aluminum hydride (270 mg, 7.00 mmol) in 30 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of diethyl ether, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0623] (SiO2-ES70 800 )-OC(CF3)2-O-Al(m / ?em-C4F9O)3-Li +

[0624] (SiO2-ES70 800 )-OC(CF3)2-O-AlH3“Li + The product obtained in the previous step was suspended in 50 ml of toluene, and 2.44 ml (17.5 mmol) of perfluoro-t / z-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, and dried in vacuum for 3 h at 50°C. Yield 5.73 g of white powder.

[0625] (SiO2-ES70 800 )-OC(CF3)2-O-Al(m / ?em-C4F9O)3-Ph3C + 1.84 g

[0626]

[0627] (SiO2-ES70 800 )-OC(CF3)2-O-Al(m / 2em-C4F9O)3“Li +suspended in 50 ml of toluene and 307 mg (1.10 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50°C. Yield 1.72 g of activating carrier as an orange powder. DRIFT (cm' 1 ): 1584 (Ph3C + ), 1484 (Ph3C + ), 1453 (Ph3C + ), 1360 (Ph3C + ), 1296, 974 (CF), 728 (CF), 704 (CF), 687 (CF).

[0628] Example C6

[0629] (81O2-E870 600 )-O-C(CP3)(CbP5)-O-A1(resh-C4P9O)3-PbzS +

[0630] (SiO2-ES70 600 )-OC(CF3)(C6F5)-OH

[0631] 1.25 g silica gel SiO2-ES70 600(~0.8 mmol / g) was placed in a Schlenk flask, 20 ml of toluene was added, and 800 mg (3.00 mmol) of perfluoroacetophenone were added. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, and dried in vacuum for 3 h at 50°C. Yield 1.15 g of white powder.

[0632] (SiO2-ES70 600 )-OC(CF3)(C6F5)-O-AlH3-Li +

[0633] 420 mg (SiO2-ES70 600 )-OC(CF3)(C6F5)-OH (0.50 mmol) was suspended in 30 ml of dry diethyl ether and a solution of freshly recrystallized lithium aluminum hydride (57 mg, 1.50 mmol) in 10 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 5 ml with diethyl ether, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0634] (

[0635]

[0636] SiO2-ES70 600 )-OC(CF3)(C6F5)-O-Al(m / 2em-C4F9O)3-Li +

[0637] (SiO2-ES70 600 )-OC(CF3)(C6F5)-O-AlH3“Li + The product obtained in the previous step was suspended in 30 ml of toluene and 6.00 ml (0.5 M in toluene, 3.00 mmol) of perfluoro-t / z-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 h at 50°C and used entirely in the next step.

[0638] (SiO2-ES70 600 )-OC(CF3)(C6F5)-O-Al(m / ?em-C4F9O)3-Ph3C +

[0639] (

[0640]

[0641] SiO2-ES70 600 )-OC(CF3)(C6F5)-O-Al(m / ?em-C4F9O)3“Li +, obtained in the previous step, was suspended in 50 ml of toluene and 280 mg (1.00 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50°C. Yield 490 mg of activating carrier as an orange powder. DRIFT (cm' 1 ): 1584 (Ph3C + ), 1485 (Ph3C + ), 1453 (Ph3C + ), 1358 (Ph3C + ), 1263, 976 (CF), 767 (CF), 726 CF), 706 (CF).

[0642] Example C7

[0643] (SiO2-ES70 600 )-OC(CF(CF3)2)2-O-Al(»2pem-C4F9O)3-Ph3C +

[0644] (SiO2-ES70 600 )-OC(CF(CF3)2)2-OH

[0645] 3.00 g silica gel SiO2-ES70 600(0.6 mmol / g) was placed in a Schlenk flask, 20 ml of toluene was added, and 1.19 g (5.40 mmol) of bis(heptafluoroisopropyl)ketone was added. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 h at 50°C, and used entirely in the next step.

[0646] (SiO2-ES70 600 )-OC(CF(CF3)2)2-O-AlH3-Li +

[0647] (SiO2-ES70 600 )-OC(CF(CF3)2)2-OH, obtained in the previous step, was suspended in 60 ml of dry diethyl ether and a solution of freshly recrystallized lithium aluminum hydride (205 mg, 5.40 mmol) in 20 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of diethyl ether, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0648]

[0649] SiO2-ES70 600 )-OC(CF(CF3)2)2-O-Al(m / ?em-C4F9O)3-Li +

[0650] (SiO2-ES70 600 )-OC(CF(CF3)2)2-O-AlH3“Li + The product obtained in the previous step was suspended in 30 ml of toluene and 21.6 ml (0.5 M in toluene, 10.8 mmol) of perfluoro-t / z-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 h at 50°C and used entirely in the next step.

[0651] (SiO2-ES70 600 )-OC(CF(CF3)2)2-O-Al(m / ?em-C4F9O)3-Ph3C +

[0652] (

[0653]

[0654] SiO2-ES70 600 )-OC(CF(CF3)2)2-O-Al(m / 2em-C4F9O)3“Li +, obtained in the previous step, was suspended in 50 ml of toluene and 1.04 g (3.60 mmol) of trityl chloride was added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 2.90 g of activating carrier as an orange powder. DRIFT (cm' 1 ): 1584 (RijsS + ), 1483 (RijsS + ), 1451 (RijsS + ), 1354 (RijsS + ), 1261, 1198, 1155, 976 (CF), 726 (CF).

[0655] Example C8

[0656] (SiO2-ES70 600 )-O-CH(C4F9)-O-Al(»2pem-C4F9O)3-Ph3C +

[0657] (SiO2-ES70 600 )-O-CH(C4F9)-OH

[0658] 2.00 g silica gel SiO2-ES70 600(0.6 mmol / g) was placed in a Schlenk flask and 1.80 g (7.20 mmol) of nonafluoropentanal was added. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 h at 50°C and used entirely in the next step.

[0659] (SiO2-ES70 600 )-O-CH(C4F9)-O-AlH3-Li +

[0660] (SiO2-ES70 600 )-O-CH(C4F9)-OH (1.20 mmol) obtained in the previous step was suspended in 40 ml of dry diethyl ether and a solution of freshly recrystallized lithium aluminum hydride (144 mg, 3.60 mmol) in 20 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of diethyl ether, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0661] (SiO2-ES70 600)-O-CH(C4F9)-O-Al(m / ?em-C4F9O)3-Li +

[0662] (SiO2-ES70 600 )-O-CH(C4F9)-O-AlH3“Li + The product obtained in the previous step was suspended in 30 ml of toluene and 14.4 ml (0.5 M in toluene, 7.20 mmol) of perfluoro-t / z-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 h at 50°C and used entirely in the next step.

[0663] (SiO2-ES70 600 )-O-CH(C4F9)-O-Al(m / ?em-C4F9O)3-Ph3C +

[0664] (

[0665]

[0666] SiO2-ES70 600 )-O-CH(C4F9)-O-Al(m / 2em-C4F9O)3-Li +, obtained in the previous step, was suspended in 50 ml of toluene and 680 mg (2.40 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 1.92 g of activating carrier as an orange powder. DRIFT (cm' 1 ): 1584 (RijsS + ), 1485 (RijsS + ), 1453 (RijsS + ), 1360 (RijsS + ), 1297, 976 (CF), 879 (CF), 741, 728 (CF), 704 (CF), 689 (CF).

[0667] Example C9

[0668] (

[0669]

[0670] SiO2-ES70 600 )-OC(CF3)2-OB(»^em-C4F9O)3-Ph3C +

[0671] (SiO2-ES70 600 )-OC(CF3)2-O-BH3-Li +

[0672] 500 mg (SiO2-ES70 600)-OC(CF3)2-OH, prepared as described in Example C1, was suspended in 40 ml of a mixture of dry diethyl ether and THF (1:1 vol.) and lithium borohydride (17.0 mg, 0.75 mmol) was added with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of diethyl ether, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0673] (SiO2-ES70 600 )-OC(CF3)2-OB(m / ?em-C4F9O)3-Li(SiO2-ES70 600 )-OC(CF3)2-O-BH3 - Li + The product obtained in the previous step was suspended in 30 ml of toluene and 3 ml (0.5 M in toluene, 1.50 mmol) of perfluoro-t / z-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 hours, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 hours at 50°C and used entirely in the next step.

[0674] (

[0675]

[0676] SiO2-ES70 600 )-OC(CF3)2-OB(m / ?em-C4F9O)3-Ph3C +

[0677] (SiO2-ES70 600 )-OC(CF3)2-OB(m / 2em-C4F9O)3“Li + , obtained in the previous step, was suspended in 50 ml of toluene and 210 mg (0.75 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 510 mg of activating carrier as an orange powder. DRIFT (cm' 1 ): 1492 (RijsS + ), 1405 (RijsS + ), 1384 (RijsS + ), 1287, 907 (CF), 745 (CF), 702 (CF), 693 (CF).

[0678] Example C10

[0679] (SiO2-ES70 600 )-OC(CF3)(C6F5)-OY(»2pem-C4F9O)3-2-MePhNHMe2 +

[0680] (SiO2-ES70 600 )-OC(CF3)2-OY(2-CH2PhNMe2)2(2-MePhNMe2)

[0681] 1.00 g silica gel SiO2-ES70 600 (~0.6 mmol / g) was suspended in 30 mL of toluene and tris(2-(dimethylamino)benzyl)yttrium (350 mg, 0.70 mmol) was added with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 7 mL of toluene, dried in vacuum for 3 h at 50°C and used entirely in the next step.

[0682] (SiO2-ES70 600 )-OC(CF3)(C6F5)-OY(m / 2em-C4F9O)3-2-MePhNHMe2 +

[0683] 500 mg of OC(CF3)2-OY(2-CH2PhNMe2)2(2-MePhNMe2), obtained in the previous step, were suspended in 30 ml of toluene and 1.80 ml (0.5 M in toluene, 0.90 mmol) of perfluoro-t / zet-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 5 ml with toluene and dried in vacuum for 3 h at 50°C. Yield 440 mg of activating carrier as a beige powder. DRIFT (cm' 1 ): 1664, 1621, 1494, 1377, 971 (CF), 727 (CF).

[0684] Example SI

[0685] (81O2-E870 600 )-O-S(SRZ)2-O-A1((SRZ))2SNO)Z-RZS +

[0686] (SiO2-ES70 600 )-OC(CF3)2-O-Al((CF3))2CHO)3-Li +

[0687] 500 mg (SiO2-ES70 600 )-OC(CF3)2-O-AlH3“Li +, obtained as described in Example C1, was suspended in 20 ml of toluene and 472 μl (4.50 mmol) of 1,1,1,3,3,3-hexafluoropropan-2-ol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0688] (SiO2-ES70 600 )-OC(CF3)2-O-Al((CF3))2CHO)3-Ph3C +

[0689] (SiO2-ES70 600 )-OC(CF3)2-O-Al((CF3))2CHO)3“Li +, obtained in the previous step, was suspended in 20 ml of toluene and 280 mg (1.00 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 470 mg of activating carrier as an orange powder. DRIFT (cm' 1 ): 1584 (Ph3C + ), 1485 (Ph3C + ), 1452 (Ph3C + ), 1360 (Ph3C + ), 1295, 890 (CF), 724 (CF), 704 (CF), 687 (CF).

[0690] Example C12

[0691] (8Ю2-Е870 60 ^O-C(CP3)2-O-A1((4-Me-SbH4)C(CP3)2O)3-P113C +

[0692] (SiO2-ES70 600 )-OC(CF3)2-O-Al(^-Tol(CF3))2CO)3-Li +

[0693] 500 mg (SiO2-ES70 600 )-OC(CF3)2-O-AlH3“Li +, obtained as described in Example C1, was suspended in 20 ml of toluene and 390 mg (1.50 mmol) of 1,1,1,3,3,3-hexafluoro-2-(i-tolyl)propan-2-ol were added with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene and dried in vacuum for 3 h at 50°C and used entirely in the next step. (SiO2-ES70 600 )-OC(CF3)2-O-Al((4-Me-C6H4)C(CF3)2O)3-Ph3C + (SiO2-ES70 600 )-OC(CF3)2-O-Al((4-Me-C6H4)C(CF3)2O)3-Li + , obtained in the previous step, was suspended in 20 ml of toluene and 280 mg (1.00 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtering on a sintered glass filter, washed 3 x 10 ml with toluene, then with 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 481 mg of activating carrier as an orange powder. DRIFT (cm'1 ): 1584 (Ph3C + ), 1483 (Ph3C + ), 1451 (Ph3C + ), 1360 (Ph3C + ), 1297, 974, 944, 885 (CF), 743 (CF), 730, 702 (CF), 687 (CF).

[0694] Example C13

[0695] (SiO2-ES70 60 OC(CF3)2-O-Al(C6F5O)3-Ph3C +

[0696] (SiO2-ES70 600 )-OC(CF3)2-O-Al(C6F5O)3-Li +

[0697] 1.80 g (SiO2-ES70 600 )-OC(CF3)2-O-AlH3“Li + , obtained as described in Example C1, was suspended in 20 ml of toluene and 450 μl (4.32 mmol) of perfluorophenol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0698] (SiO2-ES70 600 )-OC(CF3)2-O-Al(C6F5O)3-Ph3C +

[0699] (SiO2-ES70600 )-OC(CF3)2-O-Al(C6F5O)3“Li + , obtained in the previous step, was suspended in 40 ml of toluene and 605 mg (2.16 mmol) of trityl chloride were added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 1.71 g of activating carrier as an orange powder. DRIFT (cm' 1 ): 1630, 1584, 1530, 1511, 1483, 1451, 1358, 1295, 989 (CF), 704 (CF).

[0700] Example C14

[0701] (SiO2-ES70 800 )-OC(CF3)2-O-Al(OC(CF3)2-C(CF3)2-O)i,5-Ph3C(SiO2-ES70 800 )-OC(CF3)2-OH

[0702] 3.00 g silica gel SiO2-ES70 800(0.6 mmol / g) was placed in a Schlenk flask, the argon atmosphere was replaced with an atmosphere of perfluoroacetone, the silica gel was kept under a constant pressure (1 atm) of perfluoroacetone for 4 h, and then kept in a vacuum for 2 h at 50°C and completely used in the next step.

[0703] (SiO2-ES70 800 )-OC(CF3)2-O-AlH3 – Li +

[0704] (SiO2-ES70 800 )-OC(CF3)2-OH obtained in the previous step was suspended in 70 ml of dry diethyl ether and a solution of freshly recrystallized lithium aluminum hydride (144 mg, 3.60 mmol) in 20 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of diethyl ether, dried in vacuo for 3 h at 50°C, and used entirely in the next step.

[0705] (SiO2-ES70 800 )-OC(CF3)2-O-Al(O-CF2-CF2-O)i,5-Li+

[0706] (SiO2-ES70 800 )-OC(CF3)2-O-AlH3“Li + The product obtained in the previous step was suspended in 50 ml of toluene, and 480 μl (2.70 mmol) of perfluoropinacol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuum for 3 h at 50°C, and used entirely in the next step.

[0707] (SiO2-ES70 800 )-OC(CF3)2-O-Al(O-CF2-CF2-O)i,5-Ph3C +

[0708] (SiO2-ES70 800 )-OC(CF3)2-O-Al(O-CF2-CF2-O)i,5-Li +, obtained in the previous step, was suspended in 50 ml of toluene and 1.00 g (3.60 mmol) of trityl chloride was added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml with toluene, then 10 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 2.81 g of activating carrier as an orange powder. DRIFT (cm -1 ): 1621, 1584 (Ph3C + ), 1484 (Ph3C + ), 1453 (Ph3C + ), 1360 (Ph3C + ), 948 (CF), 747, 724 (CF), 706 (CF), 689 (CF).

[0709] Example C15

[0710] (SiO2-ES70 600 )-OC(CF3)2-O-Al(M3o-C3H7O)(»^em-C4F9O)2-PhNHMe2 + (SiO2-ES70 600 )-OC(CF3)2-O-Al(w3o-C3H7O)2

[0711] 3.33 g (SiO2-ES70 600)-OC(CF3)2-OH, obtained as described in Example C1, was suspended in 100 ml of toluene and 410 mg of aluminum isopropoxide (4.00 mmol) was added with stirring. The reaction mixture was stirred for 12 h at 100°C, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml of toluene and dried in vacuum for 3 h at 50°C. Yield 3.37 g of white powder.

[0712] (SiO2-ES70 600 )-OC(CF3)2-O-Al(w3o-C3H7O)(m / ?em-C4F9O)2-PhNHMe2 +

[0713] 3.37 g (8Ю2-Е870 600)-O-C(CP3)2-O-Al(r / 3-C3H7O)2 was suspended in 50 ml of toluene and 507 μl of A, A-dimethyl aniline (4.00 mmol) were added with stirring, followed by dropwise addition of 2.23 ml (16.0 mmol) of perfluoro-t / zet-butanol. The reaction mixture was stirred for 12 h, after which the silica gel was filtered on a sintered glass filter and washed with 3 x 20 ml of toluene and dried in vacuum for 3 h at 50°C. Yield 3.51 g of activating support as a purple powder. DRIFT (cm -1 ): 2981 (NH + ), 2940 (alkyl), 2882 (alkyl), 1496, 1379, 1349, 1297, 947 (CF), 728 (CF), 687 (CF).

[0714] Example C16

[0715] (SiO2-ES70 600 )-OC(CF3)2-O-AlF(m / ,em-C4F9O)(m / ,em-C4F9OH)

[0716] (SiO2-ES70 600 )-OC(CF3)2-O-Al(Et)F

[0717] 500 mg (SiO2-ES70 600)-OC(CF3)2-OH, prepared as described in Example C1, was suspended in 40 ml of toluene and diethylaluminum fluoride (128 mg, 1.25 mmol) was added with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed with 3 x 10 ml of toluene, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0718] (SiO2-ES70 600 )-OC(CF3)2-O-AlF(m / 2em-C4F9O)(m / 2em-C4F9OH)

[0719] (SiO2-ES70 600 )-OC(CF3)2-O-Al(Et)F obtained in the previous step was suspended in 30 ml of toluene and 3.00 ml (0.5 M in toluene, 1.50 mmol) of perfluoro-tert-butanol were added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 5 ml with toluene and dried in vacuum for 3 h at 50 °C. Yield 480 mg of activating carrier as a beige powder. DRIFT (cm -1): 1299, 976 (CF), 728 (CF), 688 (CF).

[0720] Example C17

[0721] (SiO2-ES70 600 )-OC(CF3)2-O-Al(»2pem-C4F9O)2(»^em-C4F9OH)

[0722] 1.80 g (SiO2-ES70 600)-OC(CF3)2-OH, prepared as described in Example C1, was suspended in 20 mL of toluene, cooled to 0°C, and 1.80 mL of a trimethylaluminum solution (3.60 mmol, 2.0 M in heptane) was added with stirring. The reaction mixture was stirred for 2 h at room temperature, after which the precipitate was separated by filtration on a sintered glass filter, washed with 2 x 10 mL of toluene, then 2 x 10 mL of hexane, and then resuspended in 20 mL of toluene and 560 µL of perfluoro-t / zet-butanol (4.02 mmol) was added with stirring. The reaction mixture was stirred for 1 h at room temperature, then 2 h at 80°C, after which the precipitate was separated by filtration on a glass frit, washed with 2 x 10 ml of toluene, then 2 x 10 ml of hexane and dried in vacuum for 3 h at 50°C. Yield 2.24 g of activating carrier as a red-brown powder. DRIFT (cm -1 ): 1593, 1353, 1300, 978 (CF), 728 (CF), 726 (CF).

[0723] Example C18

[0724] (81O2-E870600 )-O-C(CP3)2-O-B(CbP5)z-PbzC +

[0725] 300 mg (SiO2-ES70 600 )-OC(CF3)2-OH, prepared as described in Example C1, was suspended in 20 mL of hexane and a solution of n-butyl lithium (1.8 mL of 0.1 M in hexane, 0.18 mmol) was added with stirring at -78°C. The reaction mixture was stirred for 1 h at room temperature, then evaporated in vacuo, and 5 mL of toluene and 5 mL of diethyl ether were added to the residue. The resulting mixture was cooled to -78°C and 102 mg of tris(pentafluorophenyl)borane (0.198 mmol) was added. The resulting suspension was stirred for 12 h at room temperature, after which 101 mg of trityl chloride (0.36 mmol) were added. The reaction mixture was stirred for 2 h at room temperature, after which the precipitate was separated by filtration on a glass frit, washed with 3 x 10 ml of toluene and dried in vacuum for 3 h at 50°C. Yield 270 mg of activating carrier as a yellow powder. DRIFT (cm' 1): 1649, 1520, 1489, 1470, 1392, 1338, 747 (CF), 723 (CF), 704 (CF).

[0726] Example C19

[0727] (SiO2-ES70 600 )-OC(CF3)2-O-Al(»2pem-C4F9O)3-PhNHMe2 +

[0728] 5.00 g (SiO2-ES70 600 )-OC(CF3)2-O-Al(m / 2em-C4F9O)3 - Li + , obtained as described in Example C1, was suspended in 50 ml of dichloromethane and 470 mg (3.00 mmol) of N,N-dimethylaniline hydrochloride were added in one portion with stirring. The reaction mixture was stirred for 12 hours, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 10 ml of dichloromethane, then 10 ml of hexane and dried in vacuum for 3 hours at 50°C. Yield 5.1 g of activating support as a white powder. DRIFT (cm -1 ): 3073 (NH + ), 1682, 1496, 1371, 1351, 1297, 974 (CF), 728 (CF), 689 (CF).

[0729] Example C20

[0730] (SiO2-ES70 600)-OC(CF3)2-O-Al(»2pem-C4F9O)3-[ffiu2Al(PhNMe2)2] +

[0731] 1.00 g (SiO2-ES70 600 )-OC(CF3)2-O-Al(m / 2em-C4F9O)3 - PhNHMe2 + , obtained as described in Example C 19, was suspended in 10 ml of toluene and 127 μl (1.00 mmol) of L-dimethylaniline and 252 μl (1.00 mmol) of TIBA were added with stirring. The reaction mixture was stirred for 1 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 5 ml with toluene, then 5 ml of hexane and dried in vacuum for 3 h at 50°C. Yield 980 mg of activating carrier as a white powder. DRIFT (cm -1 ): 2953, 1863, 1681, 1496, 1371, 1351, 1297, 975 (CF), 881, 727 (CF), 689 (CF).

[0732] Example C21

[0733] (SiO2-ES70 600 )-OC(CF3)2-O-Al(»2pem-C4F9O)3-{H[ffiu2Al(PhNMe2)2]} +

[0734] 500 mg (SiO2-ES70 600 )-OC(CF3)2-O-Al(m / 2em-C4F9O)3'[zBu2Al(PhNMe2)2] +, obtained as described in Example C20, was suspended in 10 ml of toluene and 444 μl (2.50 mmol) of diisobutylaluminum hydride were added with stirring. The reaction mixture was stirred for 6 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 5 ml with toluene, then 5 ml of hexane and dried in vacuum for 3 h at 50°C. Yield 471 mg of activating carrier as a white powder. DRIFT (cm -1 ): 2955, 1862, 1681, 1632, 1494, 1371, 1351, 1298, 974 (CF), 728 (CF), 689 (CF).

[0735] Example C22

[0736] (SiO2-ES70 600 )-OC(CF3)2-O-Al(»2pem-C4F9O)3-ffiu2Al +

[0737] 1.86 g (SiO2-ES70 600)-OC(CF3)2-OH, prepared as described in Example C1, was suspended in 10 ml of diethyl ether and 556 μl of triisobutylaluminum (2.20 mmol) were added with stirring. The reaction mixture was stirred for 12 h at room temperature, after which the precipitate was separated by filtration on a sintered glass filter, washed with 2 x 10 ml of diethyl ether, 10 ml of hexane, and then suspended in 20 ml of toluene and 890 μl of perfluoro-t / zet-butanol (6.36 mmol) were added to the resulting suspension with stirring. The reaction mixture was stirred for 12 h at room temperature, after which the precipitate was separated by filtration on a glass frit, washed with 2 x 10 ml of toluene, 10 ml of hexane, and then suspended in 20 ml of toluene and 3.18 ml of triisobutylaluminum (3.18 mmol, 1 M in toluene) were added to the resulting suspension with stirring.The reaction mixture was stirred for 12 h at room temperature, after which the precipitate was separated by filtration on a glass frit, washed with 2 x 10 ml toluene, 10 ml hexane and dried in vacuum for 3 h at 50°C. Yield 1.89 g of activating carrier as a white powder. DRIFT (see -1 ): 2957, 2871, 1466, 1300, 1252, 978 (CF), 728 (CF).

[0738] Example of comparison CC1

[0739] (SiO2-ES70 600 )-O-Al(»^em-C4F9O)3-Ph3C +

[0740] (SiO2-ES70 600 )-O-AlH3-Li +

[0741] 300 mg silica gel SiO2-ES70 600(0.8 mmol / g) was suspended in 40 ml of dry diethyl ether and a solution of freshly recrystallized lithium aluminum hydride (23.0 mg, 0.60 mmol) in 5 ml of diethyl ether was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 5 ml with diethyl ether, dried in vacuo for 3 h at 50°C and used entirely in the next step.

[0742] (SiO2-ES70 600 )-O-Al(m / ?em-C4F9O)3-Li +

[0743] (SiO2-ES70 600 )-O-AlH3 - Li +The product obtained in the previous step was suspended in 20 ml of toluene and 1.45 ml (0.5 M in toluene, 0.72 mmol) of perfluoro-t / z-butanol was added dropwise with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 5 ml with toluene, dried in vacuum for 3 h at 50°C and used entirely in the next step.

[0744] (SiO2-ES70 600 )-O-Al(m / ?em-C4F9O)3-Ph3C +

[0745] (SiO2-ES70 600 )-O-Al(m / ?em-C4F9O)3'Li + , obtained in the previous step, was suspended in 20 ml of toluene and 100 mg (0.36 mmol) of trityl chloride was added in one portion with stirring. The reaction mixture was stirred for 12 h, after which the precipitate was separated by filtration on a sintered glass filter, washed 3 x 5 ml with toluene, then 5 ml of hexane and dried in vacuum for 3 h at 50 °C. Yield 340 mg of activating carrier as an orange powder. DRIFT (cm-1 ): 1584 (Ph3C + ), 1484 (Ph3C + ), 1453 (Ph3C + ), 1360 (Ph3C + ), 1358, 1261, 1243, 976 (CF), 726 (CF), 704 (CF).

[0746] Example of comparison CC2

[0747] (SiO2-ES70 600 )-OB(C6F5)3-Ph3C +

[0748] 4.0 g silica gel SiO2-ES70 600(0.6 mmol / g) was suspended in 20 ml of toluene and a solution of n-butyl lithium (0.912 ml, 2.5 M in hexane, 2.28 mmol) was added with stirring at -30°C. The reaction mixture was stirred for 1 h at room temperature, after which the solvents were evaporated on a vacuum pump, and 20 ml of toluene were added to the residue. The reaction mixture was cooled to -30°C and 1.18 g of tris(pentafluorophenyl)borane (2.30 mmol) was added. The resulting suspension was stirred for 12 h at room temperature, after which 700 mg of trityl chloride (2.50 mmol) was added. The reaction mixture was stirred for 3 h at room temperature, after which the precipitate was separated by filtration on a glass porous filter, washed with 4 x 10 ml of toluene, and dried in vacuum for 3 h at 50 °C. Yield 4.80 g of activating carrier as a yellow-orange powder. DRIFT (cm -1 ): 1647, 1584, 1517, 1483, 1358, 1321, 978 (CF), 747 (CF), 704 (CF).

[0749] Example of comparison of CVD

[0750] (SiO2-ES70600 )-O-Al(m / ,em-C4F9O)2(»^em-C4F9OH)

[0751] 2.00 g silica gel SiO2-ES70 600 (0.6 mmol / g) was suspended in 20 ml of toluene, cooled to 0°C, and 2.00 ml of a trimethylaluminum solution (4.00 mmol, 2.0 M in heptane) was added with stirring. The reaction mixture was stirred for 2 h at room temperature, after which the precipitate was separated by filtration on a sintered glass filter, washed with 2 x 10 ml of toluene, 2 x 10 ml of hexane, and then resuspended in 20 ml of toluene and 635 μl of perfluoro-(77) / 2c / 7?-butanol (4.56 mmol) were added with stirring. The reaction mixture was stirred for 1 h at room temperature, then for 2 h at 80°C, after which the precipitate was separated by filtration on a glass frit, washed with 2 x 10 ml of toluene, 2 x 10 ml of hexane and dried in vacuum for 3 h at 50°C. Yield 2.21 g of activating carrier as a yellow-green powder. DRIFT (cm -1 ): 1593, 1353, 1300, 978 (CF), 728 (CF).

[0752] Examples C1–C22 illustrate the possibility of using various starting compounds to obtain activating carriers. In particular:

[0753] Examples C1–C5 illustrate the possibility of using various inorganic oxides to obtain activating carriers.

[0754] Examples C6–C8 illustrate the possibility of using various polyfluorinated aldehydes and ketones to obtain activating carriers.

[0755] Examples C9, CIO, C18 illustrate the possibility of using different variants of the [metal or metalloid] atom M to obtain activating carriers.

[0756] Examples SI - C18 illustrate the possibility of using various ligands L to obtain activating carriers.

[0757] Examples of СЮ, С15, С19 - С22 illustrate the possibility of using various Ct cations y+ to obtain activating carriers.

[0758] Examples P1 - P25 and comparison examples PS1 - PS3: examples of the use of activating carriers for the polymerization of 1-hexene General information

[0759] Hexane, 1-hexene, and toluene were kept over a sodium-potassium alloy.

[0760] The residual water content was determined by Fischer titration on a Mettler Toledo C20 automatic titrator.

[0761] One transition metal complex (precatalyst) is a compound whose structure is described by the formula 04-1:

[0762]

[0763] 04-1

[0764] Another transition metal complex (precatalyst) is a compound whose structure is described by formula 04-2:

[0765]

[0766] 04-2

[0767] Another transition metal complex (precatalyst) is a compound whose structure is described by the formula CGC:

[0768]

[0769] CGCActivity is given in units of g полимера / mmol кат-ра ·h, where the number of mmolcat-ra corresponds to the number of mmol of the transition metal complex (precatalyst). Number-average molecular weight (Mn, kDa), weight-average molecular weight (M w , kDa), as well as the polydispersity index (M w / Mn) were determined by gel permeation chromatography on a Waters system (Waters 515 chromatographic pump, Waters 717plus autosampler, Polymer Laboratories PL-ELS 1000 detector, 3 PLgel Mixed-B 300×7.5 mm columns connected in series, eluent - THF, 1 ml / min, calibration using polystyrene standards ReadyCal Kit Poly(styrene) manufactured by Polymer Standards Service GmbH with molecular weights M p = 7520, 2570, 1210, 579, 246, 127, 67, 34.8, 17.8, 8.4, 3.42, and 1.62 kDa).

[0770] Example P1

[0771] In a 30 ml vial, the activating carrier (SiO2-ES70 600)-OC(CF3)2-O-A1(t / 2em-C4p9O)3'PbzC + (45 mg), obtained as described in Example C1, was suspended in 10 ml of hexane. Then, 2000 μl of 1-hexene and 200 μl of a 0.2 M solution of diisobutylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate in toluene were added with stirring. The resulting mixture was stirred for 10 min at 30°C, after which 2000 μl of a solution of complex 04-1 in toluene (1 mg / ml) were added. Polymerization was carried out for 30 min at 30°C, after which the polymerization was stopped by adding 50 ml of a 1% solution of HCl in methanol. The precipitated polymer was filtered off on a fritted glass filter, washed with methanol and dried in vacuum for 3 h at 80°C. The yield of polyhexene was 260 mg, which corresponds to an activity of 273 g / mmol h. Mn = 210 kDa, M w = 291 kDa, M w / M n = 1.4.

[0772] Example P2

[0773] The polymerization was carried out similarly to Example III, except that 3000 μl of 1-hexene were used instead of 2000 μl of 1-hexene, 500 μl of a solution of complex 04-1 in toluene (1 mg / ml) were used instead of 2000 μl of a solution of complex 04-1 in toluene (1 mg / ml), 300 μl of a 0.2 M solution of diisobutylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate in toluene were used instead of 200 μl of a 0.2 M solution of diisobutylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate in toluene, and the polymerization was carried out at 60°C. The yield of polyhexene was 331 mg, which corresponds to an activity of 1389 g / mmol h. Mn = 240 kDa, M w = 305 kDa, M w / M n = 1.3. Example of PZ

[0774] The polymerization was carried out similarly to Example P2, except that 3000 μl of 1-hexene were used instead of 2000 μl of 1-hexene, 1000 μl of a solution of complex 04-2 in toluene (1 mg / ml) were used instead of 2000 μl of a solution of complex 04-1 in toluene (1 mg / ml), and 100 μl of a 1.0 M solution of triisobutylaluminum in toluene were used instead of 200 μl of a 0.2 M solution of diisobutylaluminum 2,6-da-tert-butyl-4-methylphenolate in toluene. The yield of polyhexene was 61 mg, which corresponds to an activity of 128 g / mmol h. Mn = 67 kDa, M w = 81 kDa, M w / M n = 1.2.

[0775] Example P4

[0776] The polymerization was carried out similarly to Example III, except that (Al2O3)-O-C(CP3)2-O-Al(m / ?em-C4p9O)3-Pb3C was used as the activating carrier. + , obtained according to example C2. The yield of polyhexene was 12 mg, which corresponds to an activity of 13 g / mmol h. Mn = 281 kDa, M w = 382 kDa, M w / M n = 1.4.

[0777] Example P5

[0778] The polymerization was carried out similarly to Example III, except that (SiCh-AhCh Canac1P1O)-O-C(CP3)2-O-Al(m / 2em-C4P9O)3-Pd3C was used as the activating carrier. + , obtained according to example C3. The yield of polyhexene was 230 mg, which corresponds to an activity of 241 g / mmol h. Mn = 176 kDa, M w = 263 kDa, Mw / Mn = 1.5.

[0779] Example P6

[0780] The polymerization was carried out similarly to Example III, except that (SiC>2-Sylopol952)-OC(CF3)2-O-Al(m / 2em-C4p9O)3-Py3C was used as the activating carrier. + , obtained according to example C4. The yield of polyhexene was 310 mg, which corresponds to an activity of 325 g / mmol h. Mn = 253 kDa, M w = 363 kDa, Mw / Mn = 1.4.

[0781] Example P7

[0782] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier.800 )-OC(CF3)2-O-A1(t / 2et-C4p9O)z“RyzS + , obtained according to example C5. The yield of polyhexene was 290 mg, which corresponds to an activity of 304 g / mmol h. Mn = 140 kDa, M w = 171 kDa, Mw / Mn = 1.3.

[0783] Example P8

[0784] The polymerization was carried out similarly to Example III, except that (SiO2-E870) was used as the activating carrier. 600 )-O-C(CP3)(CbP5)-O-A1(t / 2em-C4p9O)z“PbzS + , obtained according to example C6. The yield of polyhexene was 248 mg, which corresponds to an activity of 260 g / mmol h. Mn = 208 kDa, M w = 280 kDa, Mw / Mn = 1.3.

[0785] Example P9

[0786] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF(CF3)2)2-O-A1(t / 2et-C4p9O)z“RyzS +, obtained according to example C7. The yield of polyhexene was 354 mg, which corresponds to an activity of 371 g / mmol h. Mn = 445 kDa, M w = 610 kDa, Mw / Mn = 1.4.

[0787] Example P10

[0788] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-O-CH(C4F9)-O-A1(t / 2em-C4p9O)z“RyzS + , obtained according to example C8. The yield of polyhexene was 190 mg, which corresponds to an activity of 199 g / mmol h. Mn = 184 kDa, M w = 234 kDa, Mw / Mn = 1.3.

[0789] Example P11

[0790] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-В(т / 2ет-С4р9О)з“РйзС + , obtained according to example C9. The yield of polyhexene was 31 mg, which corresponds to an activity of 33 g / mmol h. Mn = 231 kDa, M w = 286 kDa, Mw / Mn = 1.2.

[0791] Example P12

[0792] The polymerization was carried out similarly to Example III, except that (SiO2-E870) was used as the activating carrier. 600 )-О-С(Срз)(СбР5)-О-Y(m / ?em-C4F9O)3'2-MePhNHMe2 + , obtained according to the example of SY. The yield of polyhexene was 507 mg, which corresponds to an activity of 532 g / mmol h. Mn = 324 kDa, M w = 446 kDa, M w / M n = 1.4.

[0793] Example P13

[0794] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-A1((CPz))2CHO)z“RyzS + , obtained according to the SI example. The yield of polyhexene was 92 mg, which corresponds to an activity of 97 g / mmol h. Mn = 127 kDa, M w = 151 kDa, Mw / Mn = 1.2.

[0795] Example P14

[0796] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-Al((4-Me-SbH4)C(CEz)2O)z“RyzS + , obtained according to example C 12. The yield of polyhexene was 113 mg, which corresponds to an activity of 119 g / mmol h. Mn = 198 kDa, M w = 238 kDa, Mw / Mn = 1.2.

[0797] Example P15

[0798] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 800 )-OC(CF3)2-O-Al(O-С(Сез)2-С(Сез)2-О)1.5~РузС + , obtained according to example C13. The yield of polyhexene was 363 mg, which corresponds to an activity of 381 g / mmol h. Mn = 209 kDa, M w = 324 kDa, Mw / Mn = 1.5.

[0799] Example P16

[0800] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600)-OC(CF3)2-O-Al(w3o-C3H7O)(m / 2em-C4F9O)2 _ PhNHMe2 + , obtained according to example C14. The yield of polyhexene was 111 mg, which corresponds to an activity of 116 g / mmol h. Mn = 190 kDa, M w = 272 kDa, M w / M n = 1.4.

[0801] Example P17Polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-Al(w3o-C3H7O)(m / 2em-C4F9O)2 - PhNHMe2 + , obtained according to example C15. The yield of polyhexene was 526 mg, which corresponds to an activity of 552 g / mmol h. Mn = 264 kDa, M w = 352 kDa, M w / M n = 1.3.

[0802] Example P18

[0803] The polymerization was carried out similarly to Example P2, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-Al(w3o-C3H7O)(m / 2em-C4F9O)2“PhNHMe2 +, obtained according to example C15. The yield of polyhexene was 666 mg, which corresponds to an activity of 2795 g / mmol h. Mn = 607 kDa, M w = 766 kDa, M w / Mn = 1.3.

[0804] Example P19

[0805] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-AlF(m / ?em-C4F9O)(m / ?em-C4F9OH), obtained according to example C 16. The yield of polyhexene was 121 mg, which corresponds to an activity of 127 g / mmol h. Mn = 349 kDa, M w = 472 kDa, M w / M n = 1.4.

[0806] Example P20

[0807] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-Al(m / 2em-C4F9O)2(m / 2em-C4F9OH), obtained according to example C17. The yield of polyhexene was 425 mg, which corresponds to an activity of 446 g / mmol h. Mn = 532 kDa, M w= 628 kDa, M w / M n = 1.18.

[0808] Example P21

[0809] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-B(СбЕ5)з“РйзС + , obtained according to example C18. The yield of polyhexene was 167 mg, which corresponds to an activity of 475 g / mmol h. Mn = 275 kDa, M w = 354 kDa, M w / Mn = 1.3. Example P22

[0810] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-Al(m / 2em-C4F9O)3“PhNHMe2 + , obtained according to example C19. The yield of polyhexene was 162 mg, which corresponds to an activity of 170 g / mmol h. Mn = 143 kDa, M w = 185 kDa, M w / Mn= 1.3.

[0811] Example P23

[0812] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-Al(m / 2em-C4F9O)3 - [zBu2Al(PhNMe2)2] + , obtained according to example C20. The yield of polyhexene was 122 mg, which corresponds to an activity of 128 g / mmol h. Mn = 137 kDa, M w = 173 kDa, M w / M n = 1.3.

[0813] Example P24

[0814] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-Al(m / 2em-C4F9O)3“{H[zBu2Al(PhNMe2)2]} + , obtained according to example C21. The yield of polyhexene was 165 mg, which corresponds to an activity of 173 g / mmol h. Mn = 200 kDa, M w = 253 kDa, M w / M n = 1.3.

[0815] Example P25

[0816] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-Al(-C4F9O)3 - Bu2Al + , obtained according to example C22. The yield of polyhexene was 317 mg, which corresponds to an activity of 333 g / mmol h. Mn = 594 kDa, M w = 768 kDa, Mw / Mn = 1.29.

[0817] Example P26

[0818] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-OC(CF3)2-O-Al(zzz / 2ezzz-C4F9O)3“zBu2Al + , obtained according to example C22, and the CGC complex was used as a precatalyst. The yield of polyhexene was 160 mg, which corresponds to an activity of 105 g / mmol h. Mn = 15.2 kDa, M w = 19.4 kDa, M w / M n = 1.28.

[0819] Example of comparison of PS1

[0820] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier. 600 )-O-Al(m / ?em-C4F9O)3' RyzS + , obtained according to example CC1. The yield of polyhexene was 52 mg, which corresponds to an activity of 55 g / mmol h. Mn = 223 kDa, M w = 288 kDa, M w / M n = 1.3.

[0821] PS2 comparison example

[0822] The polymerization was carried out similarly to Example III, except that (S1O2-E870) was used as the activating carrier. 600 )-O-V(СбР5)з“Р11зС + , obtained according to example CC2. The yield of polyhexene was 480 mg, which corresponds to an activity of 404 g / mmol h. Mn = 100 kDa, M w = 132 kDa, M w / M n = 1.32.

[0823] Example of comparison of PSZ

[0824] The polymerization was carried out similarly to Example III, except that (SiO2-ES70) was used as the activating carrier.600 )-O-Al(m / ?em-C4F9O)2(m / ?em-C4F9OH), obtained according to example CCZ. The yield of polyhexene was 317 mg, which corresponds to an activity of 333 g / mmol h. Mn = 440 kDa, M w = 544 kDa, Mw / Mn = 1.24.

[0825] Examples K1-KZ and PP1-PPZ: examples of obtaining catalysts for the polymerization of propylene and the polymerization of propylene

[0826] Hexane, 1-hexene, and toluene were heated over sodium-potassium alloy. Residual water content was determined by Karl Fischer titration on a Mettler Toledo C20 automatic titrator.

[0827] Polymerization grade propylene was passed through a series of columns containing 4A molecular sieves, alumina, and a copper catalyst to remove traces of moisture and oxygen.

[0828] The preparation of the catalyst suspension, the introduction of hexane into the reactor, and the introduction of the catalyst suspension into the vessel for the catalyst suspension were carried out in a box with a controlled argon atmosphere (<1 ppm water, <1 ppm O2). The transition metal complex (precatalyst) is a compound whose structure is described by the formula M-1:

[0829]

[0830] A 100 ml reactor equipped with a mechanical stirrer, a pressure gauge, a 200 atm burst valve, a gas inlet, a Teflon insert (to prevent polymer fouling on the reactor walls), and a catalyst feeder were used for polymerization. The feeder consisted of a 50 ml vessel filled with gas (propylene) under a pressure exceeding the reactor pressure during polymerization, a vessel for the catalyst suspension or solution (a 2.5 ml metal tube), and a vessel containing the washing solvent (a 4.5 ml metal tube), which was located between the 50 ml vessel and the catalyst vessel and separated from them by ball valves. The catalyst suspension was fed into the reactor by squeezing the excess propylene pressure with successive openings of the valves.

[0831] Activity is given in units of g полимера / mmol кат-ра·h, where the number of mmolcat-ra corresponds to the number of mmol of the transition metal complex (precatalyst), which was taken to be equal to the number of moles of the transition metal (zirconium) determined by inductively coupled plasma atomic emission spectroscopy. Productivity is given in units of Pulmer / gcat-ra h. The melting point of the polymer was determined by differential scanning calorimetry.

[0832] Example K1

[0833] To the suspension of 500 mg of activating carrier (SiO2-ES70 600 )-OC(CF3)2-O-A1(t / 2et-C4p9O)z'RyzS +, obtained according to Example C1, in 10 ml of toluene, 3 ml of a 0.2 M solution of diisobutylaluminum 2,6-di- / 7? / 2c / 7?-butyl-4-methylphenolate in toluene (0.5 mmol / ml toluene) and 1-hexene (5 equiv. with respect to the number of moles of complex M-1) were added. The resulting mixture was stirred for 20 min at room temperature, then a solution of complex M-1 in toluene (13.5 μmol / g carrier, concentration 10 mg / ml toluene) was added dropwise. The resulting suspension was stirred for 12 h at room temperature, the precipitate was separated by filtration on a G4 glass porous filter, washed 3 x 3 ml with toluene, then 2 x 3 ml with n-hexane. The resulting catalyst was dried in vacuum at 50°C for 3 hours. The yield was 511 mg of catalyst as a gray-brown powder. According to ICP-OES, the zirconium content was 0.090 wt%.

[0834] Example K2

[0835] The catalyst was obtained similarly to Example K1, except that (SiO2-ES70) was used as the activating support.600 )-OC(CF3)2-O-Al(w3o-C3H7O)(m / 2em-C4F9O)2 _ PhNHMe2 + , obtained according to Example C15. Yield 493 mg of catalyst in the form of a grey-brown powder. According to ICP-OES, the zirconium content was 0.086 wt%.

[0836] Example of a short-term contract

[0837] The catalyst was prepared similarly to Example K1, except that complex M-1 was used at a rate of 40 μmol / g of support. The yield was 487 mg of catalyst as a gray-brown powder. According to ICP-OES, the zirconium content was 0.111 wt%.

[0838] Example PP1

[0839] A weighed portion of the catalyst powder (28.5 mg) obtained according to Example KI, 1 ml of hexane and 100 μl of a 0.2 M solution of diisobutylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate in toluene were placed in a 4 ml glass vial equipped with a magnetic stirrer and a screw cap with a PTFE gasket. The catalyst powder was then suspended in hexane with magnetic stirring for 5 min. 32 ml of hexane and 400 μl of a 0.2 M solution of diisobutylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate in toluene were placed in the reactor, and the reactor was then closed.Then the catalyst powder suspension was transferred to a suspension vessel previously connected to the reactor, the remaining volume of the vessel (about 1.5 ml) was filled with hexane, a vessel for the washing solvent was attached, which was filled with hexane (about 4.5 ml), after which a three-way valve was attached to the top of the vessel, through which a connection was provided with a 50 ml vessel intended for squeezing the catalyst suspension.

[0840] Argon in the reactor was then replaced with gaseous propylene. To do this, propylene was fed into the reactor five times at a pressure of 10 atm, then the excess pressure was released from the reactor into the air plenum. The reactor was then heated to 60°C with stirring, and at this temperature, hexane was saturated with propylene by feeding gaseous propylene through the gas inlet at a pressure of 5 atm. The propylene flow rate was controlled using a mass flow controller installed in the gaseous propylene feed line. After saturation of hexane with propylene (which was determined by the cessation of the propylene flow), the catalyst was fed into the reactor by squeezing with excess (10 atm) pressure of propylene, for which three ball valves were simultaneously opened for 5 seconds, separating the reactor volume, the vessel for the catalyst suspension, the vessel for the washing solvent and the vessel with a volume of 50 ml, pre-filled with propylene under a pressure of 10 atm and intended for squeezing the catalyst suspension into the reactor.The polymerization was then carried out for 38 minutes at 70±2°C and then stopped by stopping the propylene feed and releasing excess propylene pressure into the air plenum. The reactor was then opened, the contents transferred to a 100 ml round-bottomed flask, and the hexane was evaporated under reduced pressure on a rotary evaporator. The residue was then dried in vacuum for 3 hours at 60°C and then weighed. The polypropylene yield was 1.15 g, corresponding to an activity of 6.4 kg / mmol / g-hour and a productivity of 63.0 g / g-cat-a-hour. The polymer melting point was 150.0°C.

[0841] Example PP2

[0842] Polymerization of propylene was carried out similarly to Example PP1, except that 29.7 mg of the catalyst obtained according to Example K2 was used, and the polymerization was carried out for 20 minutes. The yield of polypropylene was 1.04 g, which corresponds to an activity of 7.8 kg / mmol / g H and a productivity of 105.1 g / GCat-a H.

[0843] The melting temperature of the polymer was 151.8°C.

[0844] Example of PPZ

[0845] A weighed portion of the catalyst powder (3.8 mg), obtained according to Example K3, 1 ml of hexane and 100 μl of a 0.2 M solution of diisobutylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate in toluene were placed in a 4 ml glass vial equipped with a magnetic stirrer and a screw cap with a PTFE gasket. Next, the catalyst powder was suspended in hexane with stirring on a magnetic stirrer for 5 min. 400 μl of a 0.2 M solution of diisobutylaluminum 2,6-di-t / ?et-butyl-4-methylphenolate in toluene were placed in the reactor, then the reactor was closed. Then the catalyst powder suspension was transferred to a vessel for adding the suspension, previously connected to the reactor, the remaining volume of the vessel (about 1.5 ml) was filled with hexane, a vessel for washing solvent was attached, which was filled with hexane (about 4.5 ml), after which a three-way valve was attached to the top of the vessel, through which a connection was provided with a 50 ml vessel intended for squeezing the catalyst suspension.

[0846] Liquid propylene was then added to the reactor. To do this, the argon in the reactor was first replaced with gaseous propylene, feeding propylene five times under a pressure of 10 atm and releasing the excess pressure from the reactor into the "air vent" each time. After this, 20 g of liquid propylene was added to the reactor from a measuring vessel. The reactor was then heated to a temperature of 55°C with stirring, after which the catalyst was fed into the reactor by squeezing it with excess (33 atm) argon pressure. For this purpose, three ball valves were simultaneously opened for 5 seconds, separating the reactor volume, the vessel for the catalyst suspension, the vessel for the washing solvent, and a 50 ml vessel, pre-filled with argon at a pressure of 33 atm and designed to squeeze the catalyst suspension into the reactor. After this, the polymerization was carried out for 22 minutes at a temperature of 69±1°C and then stopped by releasing the excess propylene into the "air vent".The reactor was then opened, the contents were transferred to a 100 ml round-bottomed flask, and the residue was dried in vacuum for 3 hours at 60°C and then weighed. The polypropylene yield was 1.56 g, corresponding to an activity of 91.8 kg / mmol / g H and a productivity of 1.12 kg / G cat-ra H.

[0847] Examples of K4, K5, KC1 and PE1, PE2, PES1: examples of obtaining catalysts for the polymerization of ethylene and the polymerization of ethylene

[0848] Hexane, 1-hexene, and toluene were maintained over sodium-potassium alloy. Residual water content was determined by Karl Fischer titration on a Mettler Toledo C20 automatic titrator. Polymerization-grade ethylene was passed through a series of columns containing 4A molecular sieves, alumina, and a copper catalyst to remove traces of moisture and oxygen.

[0849] The preparation of the catalyst suspension and the introduction of hexane and the catalyst suspension into the reactor were carried out in a box with a controlled nitrogen atmosphere (<1 ppm water, <1 ppm O2).

[0850] The transition metal complex (precatalyst) is a compound whose structure is described by formula M-2:

[0851]

[0852] A 100 ml reactor equipped with a mechanical stirrer, pressure gauge, 200 atm burst valve, gas inlet, Teflon insert (to prevent polymer fouling on the reactor walls), and a catalyst feeder were used for polymerization. The feeder consisted of a 40 ml container filled with gas (ethylene) at a pressure exceeding the reactor pressure during polymerization, and a catalyst slurry vessel—a 6.5 ml metal tube positioned between the 40 ml container and the reactor, separated from them by ball valves. The catalyst slurry was fed into the reactor by applying excess ethylene pressure while sequentially opening both valves.

[0853] ACTIVITY is given in units of Gpolymer / mmolcat-ra"h, where the number of mmolcat-ra corresponds to the number of mmol of the transition metal complex (precatalyst). Productivity is given in units of Gpolymer / gcat-ra h.

[0854] Example K4

[0855] To the suspension of 500 mg of activating carrier (SiO2-ES70 600 )-OC(CF3)2-O-Al(-C4F9O)3 - Bu2Al + , obtained according to Example C22, in 10 ml of toluene, 3 ml of a 0.2 M solution of diisobutylaluminum 2,6-di- / 7? / 2c / 7?-butyl-4-methylphenolate in toluene were added. The resulting mixture was stirred for 20 min at room temperature, then 0.364 ml of a solution of complex M-2 in toluene (concentration 10 mg / ml, 10 μmol of complex M-2) were added dropwise. The resulting suspension was stirred for 12 h at room temperature, the precipitate was separated by filtration on a G4 glass frit, washed 3 x 3 ml with toluene, then 2 x 3 ml with n-hexane. The catalyst thus obtained was dried in vacuum at 50°C for 3 h. The yield was 487 mg of catalyst as a gray-brown powder.

[0856] Example K5

[0857] The catalyst was prepared similarly to Example K4, except that (SiO2-ES70) was used as the activating support. 600 )-OC(CF3)2-O-А1( / 77 / 2с / 77-С4р9О)2( / 7? / 2с / 7?-С4р9ОН), obtained according to Example C17. Yield 492 mg of catalyst as a grey-brown powder.

[0858] Example KS1

[0859] The catalyst was prepared similarly to Example K4, except that (SiO2-ES70) was used as the activating support. 600 )-O-Al(m / 2em-C4F9O)2( / 77 / 2e / 77-C4F9OH), obtained according to Example CC3. Yield 489 mg of catalyst as a grey-brown powder.

[0860] Example PE1

[0861] A weighed portion of the catalyst powder (34.3 mg) obtained according to Example K4, 4 ml of hexane and 100 μl of a 0.2 M solution of diisobutylaluminum 2,6-di- / 7? / 2c / 7?-butyl-4-methylphenolate in toluene were placed in a 4 ml glass tube equipped with a magnetic stirrer and a screw cap with a PTFE gasket. Then, the catalyst powder was suspended in hexane with stirring on a magnetic stirrer for 10 min. 32 ml of hexane and 400 μl of a 0.2 M solution of diisobutylaluminum 2,6-di- / 7? / 2c / 7?-butyl-4-methylphenolate in toluene were placed in the reactor, then the reactor was closed. The catalyst powder suspension was then transferred to a suspension vessel previously connected to the reactor, the remaining volume of the vessel (about 2 ml) was filled with hexane, and a vessel for gaseous ethylene was connected.

[0862] The argon in the reactor was then replaced with gaseous ethylene. To do this, ethylene was fed into the reactor five times at a pressure of 10 atm, then the excess pressure was released from the reactor into the air vent. Similarly, a vessel for forcing the catalyst suspension into the reactor was filled with ethylene, after which gaseous ethylene was left in it at a pressure of 10 atm. The reactor was then heated to 60°C with stirring, and at this temperature, hexane was saturated with ethylene, feeding gaseous ethylene through the gas inlet at a pressure of 5 atm. The ethylene flow rate was controlled using a mass flow controller installed in the gaseous ethylene feed line. After saturating the hexane with ethylene (which was determined by the cessation of the ethylene flow), the catalyst was introduced into the reactor by squeezing it with excess (10 atm) ethylene pressure, for which two ball valves on the vessel containing the catalyst suspension were simultaneously opened for 2 seconds.The polymerization was then carried out for 24.8 minutes at 70±2°C, after which it was stopped by stopping the ethylene feed and releasing the excess ethylene pressure into the air plenum. The reactor was then opened, the contents transferred to a 100 ml round-bottomed flask, and the hexane was evaporated under reduced pressure on a rotary evaporator. The residue was then dried in vacuum for 3 hours at 60°C and then weighed. The polyethylene yield was 1.31 g, corresponding to an activity of 4.62 kg / mmol. кат-ра ·h and productivity of 92.4 g / g кат-ра ·h.

[0863] Example PE2

[0864] Ethylene polymerization was carried out similarly to Example PE 1, except that 31.6 mg of the catalyst obtained according to Example K5 was used, and the polymerization was carried out for 24.9 min. The yield of polypropylene was 0.72 g, which corresponds to an activity of 2.75 kg / mmol. кат-ра ·h and productivity of 54.9 g / g кат-ра ·h.

[0865] Example PES1

[0866] Ethylene polymerization was carried out similarly to Example PE 1, except that 32.0 mg of the catalyst obtained according to Example KC1 was used, and the polymerization was carried out for 25.5 minutes. The yield of polypropylene was 0.56 g, which corresponds to an activity of 2.06 kg / mmol. кат-ра ·h and productivity of 41.2 g / g кат-ра ·h.

[0867] Examples Ш - П25 illustrate the possibility of using activating supports for the activation of transition metal complexes (precatalysts) to form olefin polymerization catalysts and olefin polymerization on the resulting catalysts. In particular:

[0868] Examples K1 - K5 illustrate the possibility of using activating supports to obtain olefin polymerization catalysts.

[0869] Examples PP1, PP2, PE1, PE2 illustrate the possibility of using olefin polymerization catalysts obtained with the help of activating supports for the polymerization of olefins in a solvent medium. Example PP3 illustrates the possibility of using olefin polymerization catalysts obtained with the help of activating supports for the polymerization of olefins in a liquid monomer medium.

[0870] Comparison of polymerization activity of catalysts in examples

[0871] Example P1 (activating carrier according to example C1, (SiO2-ES70 600 )-O-C(SRz)2-O-A1(t / 2et-C4p9O)z'RyzS + ) and Example of comparison PS1 (activating carrier according to Example of comparison CC1 (81O2-E870 600 )-O-A1(t / 2et-S4p9O)z'RyzS + ), Example P20 (activating carrier according to example C 17, (SiO2-ES70 600 )-O-C(CP3)2-O-A1( / 77 / 2c / 7?-C4p9O)2(tert-C4p9OH)) and Example of comparison of PSZ (activating carrier according to Example of comparison of CCZ, (SiO2-ES70 600)-O-Al(m / 2em-C4F9O)2(m / 2em-C4F9OH)),

[0872] Example P21 (activating carrier according to example C 18, (SiO2-ES70 600 )-O-C(SRz)2-O-B(SbR5)z“RyzS + ) and Comparison example PS2 (activating carrier according to Comparison example CC2, (81O2-E870 600 )-O-V(СбР5)з“РйзС + ),

[0873] Examples PE1 (catalyst according to example K4, obtained using the activating support according to example C22, (SiO2-ES70 600 )-OC(CF3)2-O-AI( / 7? / 2c / 77-C4F9O)3-Bu2Al + ), PE2 (catalyst according to example K5, obtained using an activating carrier according to example C17, (SiO2-ES70 600 )-OC(CF3)2-O-AI( / 7? / 2c / 77-C4p9O)2( / m7 / 2e / 77-C4p9OH)) and Comparison Example PES1 (catalyst according to Comparison Example KC1, obtained using the activating support according to Comparison Example CC3, (SiO2-ES70 600 )-O-Al(m / 2em-C4F9O)2(m / 2em-C4F9OH))

[0874] — allow us to conclude that the activating carriers obtained according to the proposed method form more active catalysts for the polymerization of olefins compared to the activating carriers known from the prior art.

Claims

CLAUSES OF THE INVENTION 1. Compound of general formula (I): support - O - A (I), where the support is a solid substrate of an inorganic oxide, which is silica gel, aluminum oxide or aluminosilicate; And independently represent a functional group of general formula (II) bound to the oxygen atom of the substrate surface: [C(R 1 )(R 2 )–O–ML n ] z– (Ct y+ ) z / y (II), where R 1 and R 2 independently selected from the group consisting of a hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C6 aryl, halogen-substituted C1-C20 alkyl, halogen-substituted C3-C20 cycloalkyl and halogen-substituted C6-C6 aryl, wherein at least one of the R groups 1 and R 2 is a polyfluorinated C1-C20 alkyl, polyfluorinated C3-C20 cycloalkyl, or polyfluorinated C6-C20 aryl, where R 1 and R 2can be linked covalently to each other to form a cycle; M is selected from the group consisting of an atom of aluminum, gallium, boron, a transition metal of group 3, and a lanthanide; each L independently represents a ligand selected from the group consisting of an electron-donating ligand capable of forming a coordinate bond with the M atom, a hydrogen atom, C1-C20 alkyl, C6-C6 aryl, halogen-substituted C6-C6 aryl, a halogen atom, an oxygen atom, OR 3 , OC(O)R 3 , OSO2R 3 , C2-C20 dialkylamino groups, C6-C20 diarylamino groups, C4-C20 bis(dialkylsilyl)amino groups, C4-C20 bis(trialkylsilyl)amino groups and cyano groups, where R 3 independently selected from the group consisting of C1-C20 alkyl, C6-C6 aryl, halogen-substituted C1-C20 alkyl, halogen-substituted C6-C6 aryl, and halogen-substituted C7-C20 arylalkyl, each of which may be substituted with C1-C20 alkyl; moreover, any ligands L can be linked by covalent bonds to each other; n is 2, 3, or 4; z is equal to 0 or 1; in this case, when z is equal to 0, Ct y+ is absent, and when z is 1, Ct y+ is a cation capable of converting a neutral transition metal complex into a cationic complex capable of catalyzing the polymerization of olefins, with a charge y, where y is 1 or 2; in this case, any functional groups A can be linked by covalent bonds to each other.

2. The compound according to claim 1, wherein the functional group A is a functional group of the general formula (III): QR^R^-O-MXiQm (III), where M, R 1 and R 2 are as defined in paragraph 1; each X independently represents a ligand selected from the group consisting of a hydrogen atom, C1-C20 alkyl, C6-C6 aryl, halogen-substituted C6-C6 aryl, halogen atom, oxygen atom, OR 3, OC(O)R 3 and OSO2R 3 ; where R 3 independently selected from the group consisting of C1-C20 alkyl, C6-C6 aryl, halogen-substituted C1-C20 alkyl, halogen-substituted C6-C6 aryl, and halogen-substituted C7-C20 arylalkyl, each of which may be substituted with C1-C20 alkyl; each Q is independently selected from electron-donating ligands capable of forming a coordination bond with the M atom; m is 0, 1 or 2; in this case, any of X and / or Q can be covalently linked to each other to form a cycle.

3. A compound according to claim 1 or 2, wherein the electron-donating ligand capable of forming a coordination bond with the atom M is R 3 OH, R 3 2OH, R 3 3N, R 33P, a 5-membered or 6-membered aromatic nitrogen-containing heterocycle containing at least one nitrogen atom, a 5-membered or 6-membered aromatic oxygen-containing heterocycle containing at least one oxygen atom, a 5-membered or 6-membered aromatic sulfur-containing heterocycle containing at least one sulfur atom, C6-C10 aryl halide, tri(C1-C10)alkylaluminum, di(C1-C10)alkylaluminum hydride, where R 3 independently selected from the group consisting of C1-C20 alkyl, C6-C6 aryl, halogen-substituted C1-C20 alkyl, halogen-substituted C6-C6 aryl, and halogen-substituted C7-C20 arylalkyl, each of which may be substituted with C1-C20 alkyl.

4. The compound according to i. 1, in which the functional group A is a functional group of the general formula (IV): [CCR^ RyO-MXsJ'CCt^i / y CIV), where M, R 1 , R 2 , Ct y+ and y are as defined in i. 1; each X independently represents a ligand selected from the group consisting of a hydrogen atom, C1-C20 alkyl, C6-C6 aryl, halogen-substituted C6-C6 aryl, halogen atom, OR 3 , OC(O)R 3 and OSO2R 3 ; where R 3 independently selected from the group consisting of C1-C20 alkyl, C6-C6 aryl, halogen-substituted C1-C20 alkyl, halogen-substituted C6-C6 aryl, and halogen-substituted C7-C20 arylalkyl, each of which may be substituted with C1-C20 alkyl; in this case, any of the X can be covalently linked to each other to form a cycle.

5. A compound according to any one of paragraphs 2-4, wherein at least one of X is an OR group 3 , where R 3 independently selected from the group consisting of polyhalogenated C1-C20 alkyl and polyhalogenated C6-C20 aryl.

6. A compound according to any one of paragraphs 1-5, wherein M is an atom of aluminum, boron or yttrium.

7. A compound according to any one of paragraphs 1-6, wherein alkyl is C1-C10 alkyl, more preferably C1-C6 alkyl; cycloalkyl is C3-C6 cycloalkyl; and aryl is Ce-Cio aryl.

8. A compound according to any of paragraphs 1 and 3-7, where the cation Ct y+ selected from the group consisting of R 4 3C + , R 5 3NH + , R 6 2A1 + , ((R 5 3N)2A1R 6 2) + and H(R 5 3N-A1R 6 2)2 + ,where R 4 independently represent C6-C6 aryl, optionally substituted with one or more C6-C3 alkyl, and / or one or more C6-C3 alkylsilyl groups; R 5 independently selected from the group consisting of C1-C40 alkyl, C3-C20 cycloalkyl optionally substituted with one or more Ci-C3 alkyl, and C6-C6 aryl optionally substituted with one or more Ci-C3 alkyl, or a halogen atom; R 6independently selected from the group consisting of a hydrogen atom, C1-C40 alkyl, C3-C6 cycloalkyl optionally substituted with one or more C-C3 alkyl, C6-C6 aryl optionally substituted with one or more C-C3 alkyl, or a halogen atom.

9. A compound according to claim 8, wherein alkyl is C1-C20 alkyl; cycloalkyl is C3-C10 cycloalkyl; aryl is C1-C10 aryl; and hydrocarbyl is C1-C10 alkyl, more preferably C1-C6 alkyl.

10. The compound according to claim 1, in which the functional group A is a functional group of the general formula (V): C(K')(K. 2 )-O-(alkylaluminoxane) (V), where R 1 and R 2 are as defined in Sec.

1.

11. A compound according to claim 10, wherein the alkylaluminoxane is methylaluminoxane.

12. Compound of general formula (VI): support - O - A' (VI), where support is as defined in i. 1; A' independently represent a functional group of general formula (VII) bound to an oxygen atom of the substrate surface: [C(R 1 )(R 2 )-O-MLn]'(Ct' y+ )i / y (VII), where R 1 , R 2 , M, L, n, y are as defined in i. 1;Ct' y+ is a cation with a charge y, selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, and an R cation 5 mNH4-m + , where R 5 are the same as defined in paragraph 8, w is 0, 1, 2, 3 or 4, in this case, any functional groups A' can be linked by covalent bonds to each other.

13. A method for producing a compound according to any one of paragraphs 1-12, comprising the following steps: (1) modification of the substrate surface of general formula (VIII): support-(OHi- z )z '(Ct' ' y+ )z / y (VIII), where support, z and y are as defined in Sec. 1; Ct” y+ represents Ct y+ or Ct' y+ , as defined in paragraphs 1 and 12, respectively; by reaction with a carbonyl compound of general formula (IX): (R 1 )(R 2 )C=O (IX), where R 1 and R 2 are as defined in paragraph 1; with the formation of 1,1-diols derivatives of the general formula (X): support-O-[C(R 1 )(R 2 )-OH ( iz)] z '(Ct' ,y+ )z / y (X); (2) reacting 1,1-diols of general formula (X) with a compound containing at least one ML bond, where M and L are as defined in Sec. 1; with the formation of a compound of general formula (I) or (VI).

14. The method according to item 13, further comprising a substitution reaction in a functional group of general formula (II) or (VII) of at least one ligand L in the coordination sphere of an atom M with at least one ligand X, where M and L are as defined in item 1, X is as defined in either of paragraphs 2 and 4, provided that X is different from L.

15. The method according to claim 13, further comprising a substitution reaction of the cation Ct' y+ in a compound of general formula (VI), (VIII) or (X) per cation Ct y+ , where Ct y+ and Ct' y+ , are as defined in pi. 1 and 12, respectively.

16. The method according to any one of paragraphs 13-15, further comprising reacting the compound of general formula (I) with a compound containing at least one M-X bond, where M is as defined in i. 1, X is as defined in either 2 or 4.

17. Use of a compound according to any of paragraphs 1-10 as a solid activating support for an olefin polymerization catalyst.

18. A catalyst for the polymerization of olefins based on a compound according to any of paragraphs 1-11 and a precatalyst containing a neutral complex of a transition metal belonging to the classes of metallocenes, semi-metallocenes or post-metallocenes, or a cationic complex of a transition metal that is a catalyst for the polymerization of olefins.

19. A catalyst for the polymerization of olefins based on a compound according to claim 1, having the general formula (XI): support-O-[C(R 1 )(R 2 )-OMLn]' Т M + (XI), where R 1 and R 2 independently selected from the group consisting of a hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, halogen-substituted C1-C20 alkyl, halogen-substituted C3-C20 cycloalkyl and halogen-substituted C6-C20 aryl, wherein at least one of the R groups 1 and R2 is a polyfluorinated C1-C20 alkyl, polyfluorinated C3-C20 cycloalkyl, or polyfluorinated C6-C20 aryl, where R 1 and R 2 can be linked covalently to each other to form a cycle; M is selected from the group consisting of an atom of aluminum, gallium, boron, a transition metal of group 3, and a lanthanide; each L independently represents a ligand selected from the group consisting of an electron-donating ligand capable of forming a coordinate bond with the M atom, a hydrogen atom, C1-C20 alkyl, C6-C6 aryl, halogen-substituted C6-C6 aryl, a halogen atom, an oxygen atom, OR 3 , OC(O)R 3 , OSO2R 3 , C2-C20 dialkylamino groups, C6-C20 diarylamino groups, C4-C20 bis(dialkylsilyl)amino groups, C4-C20 bis(trialkylsilyl)amino groups and cyano groups, where R 3independently selected from the group consisting of C1-C20 alkyl, C6-C6 aryl, halogen-substituted C1-C20 alkyl, halogen-substituted C6-C6 aryl, and halogen-substituted C7-C20 arylalkyl, each of which may be substituted with C1-C20 alkyl; moreover, any ligands L can be linked by covalent bonds to each other; n is 2, 3, or 4; Т M + — a transition metal complex containing at least one hydrocarbyl group bound to a transition metal atom and a vacant coordination site that can be reversibly occupied by a dissociable ligand.

20. The catalyst according to item 19, where Т M + is a complex of titanium, zirconium or hafnium.

21. The catalyst according to I. 20, where the complex Т M +contains at least one ligand selected from the group consisting of a substituted or unsubstituted cyclopentadienyl ligand, a chelate ligand, and a monodentate ligand bonded to a metal atom via a nitrogen or oxygen atom.

22. A catalytic composition comprising a catalyst according to any of paragraphs 19-21 and an organoaluminum compound.

23. The composition according to art. 22, wherein the organoaluminum compound is capable of performing the function of a neutralizer of catalytic poisons.

24. The composition according to any of paragraphs 22-23, wherein the organoaluminum compound is represented by the general formula (XII): AlR 9 n OR 10 3-n (XII), where R 9 and R 10 independently selected from the group consisting of C1-C40 alkyl, C3-C20 cycloalkyl, C6-C20 aryl substituted with one or more hydrocarbyl groups, and a hydrogen atom, and n is 1, 2, or 3.

25. The composition according to item 24, where at least one of R 10 is 2,6-di-t / ?et-(C1-C20)alkylphenyl, optionally substituted with one or more substituents independently selected from the group consisting of hydrocarbyloxy group, C2-C20 dialkylamino group, C1-C40 alkyl, C3-C20 cycloalkyl and C6-C20 aryl, substituted with one or more hydrocarbyl groups.

26. A method for producing an olefin polymerization catalyst according to any of paragraphs 18-21 or a catalytic composition according to any of paragraphs 23-25, comprising reacting a compound according to any of paragraphs 1-11 with a precatalyst containing a neutral transition metal complex belonging to the classes of metallocenes, semi-metallocenes or post-metallocenes, or a cationic transition metal complex which is an olefin polymerization catalyst.

27. The method according to item 26, which includes reacting the compound according to item 2 with a precatalyst containing a cationic complex of a transition metal.

28. The method according to item 26, which comprises reacting the compound according to item 4 with a precatalyst containing a neutral transition metal complex.

29. A method for polymerizing olefins, comprising reacting a catalyst according to any of paragraphs 19-21 or a catalyst composition according to any of paragraphs 23-25 ​​with at least one olefin.

30. The method of claim 29, comprising reacting the catalyst or catalyst composition with one olefin.

31. The method of claim 29, comprising reacting the catalyst or catalyst composition with at least two olefins.

32. The method according to any one of paragraphs 29-31, wherein the olefin is ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene or vinylcyclohexane.

33. The method according to claim 31, wherein one of the olefins is ethylene and the second olefin is an alpha-olefin containing from 3 to 20 carbon atoms.

34. The method according to claim 33, wherein one of the olefins is ethylene and the second olefin is propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene or vinylcyclohexane.

35. The method of any one of paragraphs 29-34, further comprising a prepolymerization step in which the catalyst or catalyst composition is reacted with at least one olefin at a lower olefin concentration and / or temperature compared to the concentration and temperature of the olefin polymerization step.

36. The method according to claim 35, wherein the prepolymerization step comprises reacting the catalyst or catalyst composition with an alpha-olefin containing from 3 to 20 carbon atoms.

37. The method according to claim 36, wherein the alpha-olefin is 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene or vinylcyclohexane.

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