MXPA97007249A - Catalyst and process for the hydrogenation of olefines or polime - Google Patents

Abstract

The present invention relates to: Catalysts and Procedures for the Hydrogenation of Olefins or Polymers. The present invention relates to catalyst compositions which comprise at least: a) a metal compound cation of the formula [(A) (B) ML +] wherein M represents titanium, zirconium, or hafnium, wherein A and B represent binders with structure I or II. Wherein R1 independently represents the same or different hydrocarbyl groups optionally containing heteroatoms, and R3 independently represents the same or different hydrocarbyl groups that optionally contain heteroatoms, or a halide, and in which the R substituents may be options between A and B to provide a bridge, where M is an integer from 0-5, p is an integer of 0-4, and q is an integer of 0-3, where L represents the hydrogen or hydrocarbyl group that optionally they contain heteroatoms, with the prediction that if A and B are both binders with structure I and II, at least one of m, poq is at least 1, and b) a different stable anion. The present invention further relates to a process for the preparation of a catalyst composition and to a process for the catalytic hydrogenation of olefins, oligomers, polymers or copolymer

Description

CATALYST AND PROCESS FOR THE HYDROGENATION OF OLEFINS OR POLYMERS The invention relates in general to a process for the hydrogenation of olefins, and in particular to conjugated diene polymers or oligomers, and to catalysts which can be used for this, as well as to a process for the preparation of the catalysts. More particularly, the invention relates to a process for the hydrogenation of olefins or oligomers, polymers or copolymers of the conjugated diene polymers, which have one or more substituent atoms attached to one of the double bond carbon atoms, using a hydrogenation catalyst comprising at least one transition metal complex of group 4. Many catalysts are known for the hydrogenation of compounds containing double bond catalysts of unsaturated compounds, which can be classified into the two groups: 1) Heterogeneous catalysts, which generally consist of a metal such as Ni, Pd, Pt, Ru, etc. optionally deposited on a support such as carbon, silica, alumina, calcium carbonate, etc .; and (2) homogeneous catalysts such as (a) catalysts REF: 25737 Ziegler consisting of a combination of an organic salt of Ni, Co, Fe, Cr, etc. and a reducing agent such as organoaluminum compounds and the like, and (b), organometallic compounds of particular components of Ru, Rh, Ti, La, etc. US Patent No. 4,501,857 discloses a hydrogenation catalyst in which one of the compounds is a cyclopentadienyltitanium derivative - necessarily in the presence of organolithium compounds - for the hydrogenation of the olefinic double bonds of the polymers of the conjugated dienes. European Patent Application Publication Nos. 0460725, 0549063, 0434469, 0544304, 0545844 and 0601953, International Applications WO 96/18660 and WO 96/18655, and British Patent Application No. 2159819 also describe catalyst compositions of homogeneous hydrogenations containing titanium. International Application No. WO 95/25130 discloses a process for the selective hydrogenation of polymers of unsaturated compounds containing olefinic and aromatic carbon-carbon double bonds, using a catalyst complex of a metallocene compound comprising zirconium connected to two indenyl groups or substituted or unsubstituted cyclopentadienyls and two other binders selected from halogen, alkyl or lower benzyl, and an alumoxane and methylalumoxane, preferably in a molar ratio of zirconium metal to an aluminum metal in the 50-500 catalyst complex. However, as is known, in, for example, European Patent Application Publication No. 0584860, specialists or specialists in known hydrogenation processes have as a general deficiency, a block of copolymers comprising at least blocks formed by poly (conjugated dienes) in which the monomer formed had a branched alkadiene of 5 to 10 carbon atoms and has at least one alkyl substituent of one of the carbon atoms of the remaining double bonds, which can not be completely or substantially hydrogenated under the usual hydrogenation conditions. More particularly, said deficiency is the reason why the known catalysts were satisfactory for the selective hydrogenation of poly (styrene) -poly (butadiene) copolymer blocks, but not for the blocks of copolymers comprising poly (isoprene) blocks. or blocks in which the isoporene is a co-monomer. It can be appreciated that they can be established for other substituted poly (alkadienes) as well as tri or tetra substituted olefins. The deficiencies of these catalysts are not limited by the hydrogenation of the polymeric substrates as described above. Deficiencies extend or extend to low molecular weight substrates that contain similarly substituted double bonds as well, as exemplified in the work of Broene and Buchwald (J.Am. Chem. Soc. 1993, 115, 12569). In addition, the work of Mar s et al, as described in US Pat. No. 4,668,773, shows that the hydrogenation of olefinic bonds with more than two substituent atoms is indeed a very difficult reaction by which known homogeneous catalysts are not efficient. It is appreciated that there is a need for homogeneous "all purpose" catalysts to hydrogenate all types of olefinic substrates, including poly (conjugated diene) blocks in the copolymer blocks, economically with respect to costly catalysts ( by the use of low concentrations) and process times (preferably less than one hour for the hydrogenation of more than 80% of the original double bonds and preferably more than 95% and preferably more than 98%). Therefore, an object of the present invention is formed by an improved hydrogenation process and another object is formed by a catalyst composition for use in said process. As a result of an extensive search and experimentation, such a catalyst and process have been found surprisingly. Accordingly, the present invention relates to a catalyst composition which comprises at least: a) a metal compound cation of the formula [(A) (B) ML +] wherein M represents titanium, zirconium, or hafnium, where A and B represent binders with structure I or II.

Structure I structure II in which Ri independently represents the same or different hydrocarbyl groups optionally containing heteroatoms, and R3 independently represents the same or different hydrocarbyl groups that optionally contain heteroatoms, or a halide, and in which the substituent atoms R may be options between A and B to provide a bridge, where m is an integer from 0-5, p is an integer from 0-4, and q is an integer from 0-3, where L represents the group hydrogen or hydrocarbyl optionally containing heteroatoms, with the proviso that if A and B are both ligands with structure I and II, at least one of m, poq is at least 1, b) a different stable anion. Preferably the metal compound cation having structure III structure III wherein M = titanium or zirconium, wherein A = a binder with structure I or II in which Ri and R2 are independently the same or different hydrocarbyls that optionally contain a heteroatom, and R3 is a hydrocarbyl, which optionally contains a heteroatom , or a halide; R2 can be combined with Ri or R3 to form a bridge; where m is an integer from 0-5, p is an integer of 0-4, and q is an integer of 0-3, and n is an integer of 1-5; wherein L represents the hydrocarbyl group or hydrogen optionally containing heteroatoms. More preferably, R2 is a branched hydrocarbyl of 3 to 15 carbon atoms and optionally contains heteroatoms. According to the preferred additional embodiments, the present invention relates to a catalyst composition which comprises at least: (a) a cation composed of metal of the formula A "V. ^ M (+) L wherein M represents zirconium, titanium or hafnium, wherein A represents a cyclopentadienyl group of the formula an indenyl group of the formula wherein each Rx independently represents the same or different alkyl groups having from 1 to 4 carbon atoms, wherein each R 2 independently represents the same or different heavy molecular structures formed by an alkyl group, having 3 to 10 carbon atoms, an aryl group having from 6 to 20 carbon atoms, which by themselves can be optionally substituted by lower alkyl groups having from 1 to 3 carbon atoms or halogen, cycloalkyl groups having from 5 to 8 carbon atoms and which optionally can be substituted by lower alkyl group (s) having from 1 to 3 carbon atoms- or halogen, aralkyls having from 7 to 14 carbon atoms which can be optionally substituted per lower alkyl group (s) having 1 to 3 carbon atoms or halogen, or optionally substituted alkyl groups or groups containing heteroatoms, such as -Si (C? -C3 alkyls) 3, ~ Si (phenyl) 3, ~ N (phenyl) 2, ~ NH (phenyl), ~ B (phenyl) 2 and ~ B (phenoxy) 2, wherein each of the R3 independently can be selected from halogen, phenyl, which can optionally be substituted by lower alkyls (1-3 carbon atoms), lower alkoxy (1-3 carbon atoms), phenoxy, phenylalkoxy or benzyl, wherein p can be an integer from 0 to 4, where m represents an integer in the range of 1 to 5 and preferably from 3 to 5, where q represents an integer in the range of 1 to 3 and n represents an integer from 1 to 5, and preferably 1, wherein L represents hydrogen, an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 18 carbon atoms, an arylalkyl group of 7 to 24 carbon atoms, or an optionally substituted allyl group, and (b) a different stable anion. However, the present invention relates to a process for the hydrogenation of ethylenic polymers, which contain unsaturated compounds, preferably at least one of the monomers constituting the polymer comprises at least one carbon atom that has been replaced, which uses catalyst procedures specified in this point. According to the preferred additional embodiments of the catalysts, M represents zirconium or titanium, Ri represents a lower alkyl of 1 to 3 carbon atoms and more preferably methyl, m has a value of 5, and q has a value of 3, R2 represents a hydrogen or a hydrocarbyl group, n is 1, R3 represents a lower alkyl or lower alkoxy and p = 0, 1 or 2, and preferably 0. More preferably R2 is a heavy substituent atom, selected from the group consisting of phenyl, o-tolyl, 2,6-xylyl, p-tert butyl phenyl, 2,6 (isopropyl), m-phenyl dichlorophenyl, 3,5-di (tert butyl) -4-methoxy-phenyl dimethylphenyl methyl, tert butyl, iso propyl , iso butyl and cyclopentyl or hexyl cyclo, trimethylsilyl, dimethyl tert.butylsilyl, tri (phenyl) silyl, di phenyl amine, diphenyl boryl. More preferably R2 is tert butyl or trimethylsily and m = l. In the most preferred embodiments of the present catalysts L represents hydrogen, methyl, ethyl, n-propyl, n-butyl, neopentyl, dimethylphenylmethyl, benzyl, phenyl, allyl or substituted allyl and more preferably methyl. The different stable anions can be derived from a variety of boron-containing compounds.

Examples of such compounds are known from the literature, for example in Marks et al, Organometallics 1995, 14, 3135. Preferably, the different stable anions are carborane anions, conveniently a carborane anion of the formula [Bn-CH 2" Such carboranes are known and can be prepared by methods such as those of K. Shelly et al (J. Am. Chem. Soc. 107, 1985, 5955.) More preferably, anions of the formula [RB (Ar ) 3 ~] wherein Ar represents a hydrocarbyl group strongly separated from the electron, preferably a phenyl group substituted with substituent atoms strongly separated from the electron, such as halogen or alkoxy having from 1 to 3 carbon atoms or methyl substituting trihalogens. R represents Ar or a group which is typically the same represented by L, which is a hydrate group or a hydrocarbyl, optionally containing heteroatoms. More preferably the different stable anion has the formula [B (Ar) 4 ~], and Ar represents (C6F5) or 3.5 (CF3) 2C6H3 without the bonds being a definite theory it is presumed that the catalysts for the hydrogenation specified at this point they can derive their unique effectiveness from their ability to perform CH activation. This ability allows the metal alkyl species to be formed during the reaction from the alkanes and in addition can allow isomerization of substituted tri-and tetra-olefins by being disubstituted minor blocking olefins which can be rapidly hydrogenated. The catalyst compositions are typically obtained by the reaction of a metal compound of formula (A) (B) ML2, wherein A, B, M and each L independently are as defined at this point (precursor component (a)), with a salt of a different stable anion (precursor component (b)). Preferably, the salt of the different stable anion is D + [B (Ar) 4] "or B (Ar) 3 in which Ar is as defined herein and D is a cation capable of reacting with an L of the metal compound to form a DL compound. Preferably, the DL compound , the elimination product ends at this point, is not interfered with by the last hydrogenation reaction or can easily be removed from the current catalyst Examples of suitable cations D are PhNMe2H + or Ph3C + Examples of suitable elimination products are triphenyl ethane, generated by the reaction of a Group 4 of dimethyl metallocene compounds with a tritylium salt of a different anion, or methane, generated by the reaction of a group 4 of dimethyl metallocene compounds with a dimethylaniline salt of a different anion. of the precursor components (a) and (b) may typically vary in the range of 1: 5 to 5: 1 and preferably 1: 1. Further, in accordance with a further aspect, the present invention relates to a process Preparation for the preparation of a catalyst composition, which comprises reacting a metal compound of the formula (A) (B) ML2 as defined herein, with a salt of a different stable anion as defined herein. The catalyst compositions of the present invention can be prepared first by the current hydrogenation process, i.e. making contact with the hydrogen and the polymer containing the unsaturated ethylenic compound, or they can be prepared in situ, ie in the presence of hydrogen and polymer cement, from which a substantial part previously formed (during completion) of the lithium compound has been removed before. It will be appreciated that in accordance with other more preferred embodiments, the formation of a readily insoluble, separable lithium compound such as lithium chloride will be simultaneously conducted and interrelated to the formation of the catalyst compounds (a) and (b) from the precursor compounds conveniently selected.

It will be appreciated that the catalyst compositions and processes for hydrogenation according to the present invention have surprisingly shown that they are capable of completing the hydrogenation of the unsaturated ethylenic compounds. In accordance, an advantage of the present hydrogenation process and catalysts is that only the homopolymers or blocks of copolymers containing linearly polymerized conjugated dienes can be (selectively) hydrogenated, but also the homopolymers of branched conjugated dienes or blocks of copolymers having at least one poly (aromatic monovinyl) block and at least one poly (monovinyl aromatic) block and at least one poly (branched conjugated diene) block, and preferably poly (isoprene) homopolymers or poly (styrene) -poly ( isoprenes), can be effectively hydrogenated with a very high selectivity with respect to unsaturated olefinic compounds. The hydrogenation grades of 95% or more of the original unsaturated olefinic compounds can be rejected for periods of at least 3 hours and preferably from 0.5 to 1 hour. The hydrogenation process can be carried out at partial hydrogen pressures in the range from about 0.1 to 100 bar and preferably from 1-35 bar. Included in the above diene polymers, branched conjugates, are the branched conjugated diene homopolymers and the copolymers produced from branched conjugated dienes and unbranched conjugated dienes or at least one branched conjugated diene and at least one olein copolymerizable with the conjugated diene branched Examples of conjugated dienes used for the production of these oligomers or branched conjugated diene polymers are conjugated dienes having 5-12 carbon atoms. Specific examples are isoprene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and chloroprene. . In particular, from the aspect of the manufacture of hydrogenated elastomers with industrial advantages, the isoprene homopolymers, the copolymer blocks comprise at least one block derived from an isoprene monomer alone or optionally mixed with any other conveniently conjugated linear diene, They can be prepared in an economically attractive way. However, said blocks of copolymers may comprise addition blocks of other linear and / or branched linear dienes and / or blocks of pure or slightly functional monovinyl aromatic monomers or random polymerized blocks of isoprene and suitable monovinyl aromatic monomers and styrenes. The hydrocarbon solvents used in the hydrogenation reaction may be aliphatic hydrocarbons, for example, pentane, hexane, heptane, octane, etc.; alicyclic hydrocarbons for example, cyclopentane, cyclopentane methyl, cyclohexane, etc. Or aromatic solvents such as toluene or preferably bromobenzene. There are no restrictions as to the concentration of polymers to carry out the hydrogenation reaction of the present invention, usually, the concentration of the polymers is 1-30% by weight, and preferably 3-20% by weight. The hydrogenation reaction is carried out after the addition of the hydrogenation catalyst composition under an inert gas atmosphere, for example, under nitrogen or argon, or under an atmosphere of hydrogen, by supplementary hydrogen, with or without stirring, while the temperature of the polymer solution is maintained at a specified temperature. A suitable temperature for the hydrogenation reaction is 0-150 ° C. A lower temperature of 0 ° C is not economical, since at temperatures below 0 ° C, not only the temperature of the catalyst activity is lowered, but also the hydrogenation rate is retarded. If the temperature is higher than 150 ° C, the terminal or final polymers decompose in gel. A more preferred temperature range is 10-100 ° C, and particularly more preferred is 15-75 ° C. The hydrogenation reaction is usually carried out within a period of time from 0.1 hour to 3 hours. The greater amount of the catalyst composition used and the high hydrogen pressure can shorten the reaction time. The catalyst concentrations usually applied per 100 g of polymer for hydrogenation will be in the range of 0.01 g to 1 g Zr, metal Hf or Ti, and preferably 0.19-0.75 g Zr, metal Hf or Ti per 100 g of the polymer. The invention may be illustrated by the following examples without however restricting the scope of the invention for those specific embodiments.

EXAMPLES The following precursor catalysts were prepared. (A) Preparation of Cp * Cp tBu Zr (Me) 2 where Cp * =? 5: CsMe5, Me = methyl and tBu = tert butyl, Cp = cyclopentadienyl or substituted cyclopentadienyl [Cp (Me) 5] ZrCl3 (1.763 g, 5.30 mmol) and (CptBu) Li (691 mg, 5.38 mmol) were weighed within a Schlenk flask. The flask was cooled to 196 ° C and mesitylene (50 ml) was added. The suspension was allowed to cool slowly to room temperature and subsequently heated to 120 ° C. After this, it was stirred for 22 hours at 120 ° C, the mesitylene was removed in vacuo. The yellow residue was suspended in diethyl ether (40 mL). MeLi drop (6.95 mL, 11.1 mmol) was added at room temperature. The suspension was stirred for another 18 hours at room temperature. The diethyl ether was removed in vacuo and the residue was extracted with pentane (40 mL). Filtration, concentration and crystallization at 30 ° C gave [Cp (Me) 5] (CptBu) ZrMe2 (688 mg, 1.81 mmol) as a clear white. A second recrystallization gave another portion, which, however, was contaminated with a yellow oil. The oil was partially removed by washing the crystals with two small portions of cooled pentane. The total produced: 971 mg (2.57 mmol, 52%).

(B) Preparation of Cp * .Cp [(Me) 3 Si] 2 ZrMe2. This compound was prepared in the same manner as described under (A) initially from [Cp (Me) 5] ZrCl3 and Cp [(Me) 3Si] 2, whereupon MeLi was subsequently added. (C) Preparation of Cp * Cp (tBu) TiCl2 1.09 grams of Cp * TiCl3 (3.77 mmol) were dissolved in 25 mL of CH2C12 and cooled to -40 ° C. 0.53 grams of (tBu) Cp lithium (3.77 mmol) were added and the reaction mixture was slowly driven to room temperature. After being stirred for 16 hours, the reaction mixture was centrifuged and the CH2C12 was removed in vacuo. 1.39 grams of Cp * Cp (tBu) TiCl2 (98%) was obtained as a purple crystalline compound.

^ -NMR (CD2C12): d 6.16 (t, 3 JHH = 2.7 Hz, 2, CpH), 5.89 t, 3 JHH = 2.7 Hz, 2cPh); 1.9 (s, 15, C5Me5); 1.28 (S, 9, C (CH3) 3) 3 13 C-NMR (CD2C12): d 149.8 (CptBUIPSO); 129.5 (C5Me5); 120.9 (CptBU); 114.2 (CptBU); 34.2 (C (CH3) 3); 30.5 (C (CH3) 3); 13.1 (C5 (Me) 5) (D) Preparation of C? *. Cp (tBU) Ti Me2 846 mg of Cp * Cp (tBU) TiCl2 (2.28 mmol) in 20 mL of diethyl ether were cooled to -78 ° C . 2.85 mL of a 1.6 M solution of MeLi in ether (4.55 mmol) was added. The reaction mixture was left to warm slowly at room temperature. The colored reaction mixture of yellow was evaporated to dryness and extracted with pentane. Removal of pentane gave 0.51 grams (67%) of Cp * Cp (tBu) TiMe2 as colored crystals of yellow. ^ -NRM (C5D6); d 5.90 (t, 3JHH = .6 Hz, 2, CpH), 5.36 (t, 3JHH = 2.6 HZ, 2, CpH); 1.68 (s, 15, C5Me5); 1.28 (s, 9, C (CH3) 3); -0.15 (s, 6, Ti (CH3) 2) 13 C-NMR (C6D6): d 142.2 (CptBuipso); 119.5 (CptBu); 112.7 (C5Me5); 110.0 (CptBu); 45.6 (TiCH3); 33.6 C (CH 3) 3); 31.2 (C (CH3) 3); 11.9 (C5Me5) (E) Preparation of Cp Ind.Ti (benzyl) 2. To a suspension of 981.6 mg of CpIndTiCl2 (3.28 mmol) in 50 mL of ether was added 849 mg of Mg (CH2Ph) 2 0.5 dioxane (3.28 mmol ). The reaction was stirred overnight, filtered and evaporated to dryness. XH-NMR (C6D6) d 7.23 (d, 3 JHH = 8 Hz, 2, benzyl-Hm), 7.15 (m, H (ind), 2); 6.9 (m, H (ind) + benzyl-Hp, 6); 6.8 (d, 3 JHH = 8HZ, 2); 6.07 (d, 3HHH = 3.5 HZ, 2, CpH); 5.88 (t, 3 JHH = 3.5 HZ, 1, CpH); 5.38 (s, 5, CpH); 1.5 (AB-pattern, 2JHH = 8.9 Hz, TiCH2) 13 C-NMR (C6D6) d 153.6 (benzyloxy); 126.2; 126.1 (beniloilo); 125.7 (benzyiometa); 125.i; 121.8; 119.0 (benzyl); 116.5; 115.0 ((C5H5) 2TiBz2); 106.0; 76.9 (TiCH2) The following hydrogenation experiments were carried out: Example 1 A pressure flask was charged with 9.1 mg of Cp * Cp (tBu) ZrMe2 (24 μmol), 20.5 mg of [Ph3C] [B (C6F5) 4] (22 μmol) in 1 ml of bromobenzene, followed by 0.84 mL of 2,4,4-trimethyl-2-pentene (5.39 mmol) and 3 mL of bromobenzene. The hydrogenation was conducted for 10 minutes, under 1 bar of hydrogen at room temperature. GC analysis: 99.9% hydrogenated olefin Example 2 To a pressure flask loaded with 402 mg of polyisoprene in 2 mL of bromobenzene was added a mixture of 9.2 mg of Cp * Cp (tBu) ZrMe2 (24 μmol) and 20.6 mg of [ Ph3C] [BC6F5) 4] (22 μmol) in 1 mL of bromobenzene. The flask was placed under 1 bar of H2 and stirred for 45 min. 1 H-NMR showed the complete conversion. Example 3 A 'a pressure bottle loaded with 316 mg of polyisoprene in 2 mL of bromobenzene was added a mixture of 7.0 mg of Cp * Cp (tBu) ZrMe2 (18.5 μmol) and 14.9 mg of [PhNMe2H] [B (C6F5) 4] (18.6 μmol) in 1 mL of bromobenzene.

The bottle was placed under 1 bar of H2 and stirred for 45 minutes. • '"H-NMR showed complete conversion Example 4 To a pressure bottle loaded with 303 mg of polyisoprene in 2 mL of bromobenzene were added a mixture of 10.3 mg of Cp * C? [(Me) 3si) 2ZrMe2 ( 22 μmol) and 18. 5 mg of [Ph3C] [B (C6F5) 4] (20 μmol) in 1 mL of bromobenzene. The flask was placed under 1 bar of H2 and stirred for 16 hours. 1H-NMR showed a conversion > 98%.

Example 5 A pressure bottle was loaded with 8.5 mg of Cp * Cp (tBu) TiMe2 (25.4 μmol), 21.6 mg of [Ph3C] [B (C6F5) 4] (23.4 μmol) in 1.0 mL of bromobenzene, followed by 0.78 mL of 2, 4, 4-trimethyl-2-pentene (5.1 mmol, 200 equivalents) and 3 mL of bromobenzene. The hydrogenation was carried out for 0.5 hours under 1 bar of hydrogen. GC analysis: 80.5% hydrogenated olefin. Example 6 To a pressure bottle loaded with 273 mg of polyisopropane in 2 mL of bromobenzene were added 8. 6 mg of Cp * Cp (tBu) TiMe2 (25.7 μmol) and 21.8 mg of [Ph3C] [B (C6F5) 4] (23.7 μmol) in 1 mL of bromobenzene. The flask was placed immediately under 1 bar of H2 and stirred for 0.5 hours. 1 H-NMR showed approximately 50% conversion. Example 7 To a pressure bottle loaded with 9.5 mg of Cp * Cp (tBu) TiMe2 (28.4 μmol), 22.8 mg of [PhNMe2H] [B (C6F5) 4] (28.4 μmol) in 1.0 mL of bromobenzene, followed by 0.90 mL of 2, 4, 4-trimethyl-2- Pentene (5.8 mmol, 206 equivalents) and 3 mL of bromobenzene. The hydrogenation was carried out for 0.5 hours under 1 bar of hydrogen. GC analysis: 28% hydrogenated olefin. Example 8 To a pressure flask loaded with 11.3 mg of indenyl cyclopentadienyl titanium dibenzyl (22.2 μmol) and 18.9 mg of [Ph3C] [B (C6F5) 4] (20.5 μmol) in 1 ml of bromobenzene, 0.86 ml of , 4, 4-trimethyl-2-pentene (5.5 mmol, 200 equivalents) and 2 ml of bromobenzene. The reaction was carried out for 0.5 hours under 1 bar of hydrogen. The GC analysis showed 99% of the hydrogenated olefin. Example 9 To a pressure flask loaded with 287 mg of polyisoprene (4.2 mmol, 187 equivalents) in 2 mL of bromobenzene were added 9.6 mg of indenyl cyclopentadienyl titanium dibenzyl (23.4 μmol) and 19.9 mg of [Ph3C] [B (C6F5) ] (21.5 μmol) in 1 mL of bromobenzene. The flask was placed immediately under 1 bar of H2 and stirred for 0.5 hours. 1 H-NMR showed approximately 20% conversion.

Example 10 An NMR tube was loaded with 5.5 mg of Cp * CptBuZrMe2 (14.5 μmol), 12.6 mg of [Ph3C] [B (C6F5) 4] (13.6 μmol), 36 mg of 2, 3-dimethyl-2-buten (0.42 mmol, 30 equivalents) in 0.5 mL of bromobenzene-d5. After 1 hour, "15% of 2,3-dimethyl-2-buten was hydrogenated to 2,3-dimethylbutane (about 15 mL of H2 was added via syringe). Example 11 An NMR tube loaded with 7.3 mg of indenyl cyclopentadienyl titanium dibenzyl (17.8 μmol), 16.4 mg of [Ph3C] [B (C6F5) 4] (17.8 μmol), 83.9 mg of polyisopene (1.22 mmol, 69 equivalents) in 0.5 mL of bromobenzene-d5. After 1 hour, more than 90% of the doubonds were hydrogenated (approximately 30 mL of H2 were added via syringe). Comparative Example (a) A similar experiment as in Example 11 was performed with bis-cyclopentadienyl titanium bibencil, but the conversion of polyisoprene was not observed. Comparative Example (b) An NMR tube was loaded with 0.86 mg of indenyl cyclopentadienyl titanium dibenzyl (10.7 μmol), 5 mL of H2 and 0.5 mL of C6D6. After 1 hour, 50 mg of polyisoprene (0.73 mmol, 35 equivalents) were added to the reaction mixture together with 8 mL of H2. 1 H-NMR showed only the hydrogenation of the 1,2 doubonds. Example 12 To a pressure flask loaded with 0.86 ml of 2,4,4-trimethyl-2-β-entene-2 (5.5 mMol) and 3 ml of bromobenzene were added 6.2 mg of CptBu (1,3-Ph 2 -Me- indenyl) TiMe2 and 11.2 mg of [Ph3C +] [B (C6F5) "4] The flask was placed immediately under 1 bar of H2 and stirred for one hour.The analyzes showed 100% conversion of the olefin to 2, 4, 4-trimethylpentane Example 13 To a bottle loaded with 8.0 mg of CptBu Cp * ZrMe2 and 20.0 mg of [PhNMe2H +] [B (C6F5) ~ 4] was added 0.45 g of 1-CD3C6H9 (trideuteromethylcyclohexane) at room temperature. It was pressurized immediately with 5 bar of H2 After 45 minutes of continuous stirring, the reaction was stopped and the products analyzed. The olefin was converted by more than 98% by producing trideuteromethylcyclohexane. Example 14 To 10.7 mg of 1,1 '-ethylenebisindenyl zirconium dimethyl (EtInd2ZrMe2), (25.8 mole) (containing approximately 0.5 equivalents of diethyl ether) in an NMR tube was added 20.7 mg of [PhNMe2H] [B (C6Fs) 4 ] (25.8 μmol) in 0.5 mL of CßDsBr. To this reaction mixture was added 50 μL of 1-methylcyclohexane (423 μmol, 17 equivalents) and 3 aliquots of 4 mL of H2. After 1.5 hours >; 90% was hydrogenated to methylcyclohexane (XH-NMR). Example 15 8.0 mg of 1,1 '-dimethylsilylbisindenyl zirconium dimethyl (Me2SiInd2ZrMe2), (19.6 μmol) and 15.6 mg of [PhNMe2H] [B (C6F5) 4] (19.6 μmol) were mixed in a tube NMR with 0.5 mL of C6D5Br. 16 μL of 1-methylcyclohexane and 5 mL of H2 were added. The slow hydrogenation was observed for methylcyclohexane ("60% conversion) Example 16 9.5 mg of 1, 1'-ethylenebisindenyl zirconium dibenzyl (EtInd2ZrBz2), (17.9- μmol) and 14.3 mg of [PhNMe2H] [B (C6F5) 4] (17.9 μmol) were produced in 0.5 ml of CßDFsBr (NMR tube). 100 μL of 1-methylcyclohexane (846 mol, 47 equivalents) were added. The 5 μmL portions of H2 were added via syringe. Hydrogenation for methylcyclohexane was observed. A conversion of 98% was carried out around one hour.

Example 17 An NMR tube loaded with 4. 2 mg of [Cp (tBu)] 2ZrMe2 (11.5 μmol), 10 mg of [PhNMe2H] [B (C6F5) 4] (12.5 μmol) in 0.5 ml of bromobenzene-d5. To this solution was added 120 mg of 2,4,4-trimethyl-2-pentene (1.07 mmol). In one hour 30 ml of H2 was added via syringe. The XH-NMR spectrum of the solution showed a complete conversion of 2, 4, 4-trimetii-2-pentene for 2,2,4-trimethylpentane. Example 18 An NMR tube was loaded with 4 mg of [Cp (nBu)] 2ZrMe2 (11 μmol), 8.9 mg of [PhNMe2H] [B (C6F5) 4] (11.1 μmol) in 0.5 ml of bromobenzene-d5. 121 mg of 1-methylcyclohexane (1.26 mmol) were added to this solution. In 1 hour 35 ml of H2 were added via syringe. The XH-NMR spectrum of the solution showed the complete conversion of 1-methylcyclohexane to methylcyclohexane. Example 19 To a solution of 10 mg [Cp (nBu)] 2ZrMe2 (27.5 μmol) in 0.5 g of benzene-d6 was mixed with 22.5 mg [PhNMe2H] [B (C6F5) 4] (28 μmol) in 1.6 g of toluene . An NMR tube was loaded with one third of this mixture and 128 mg of 1-methyl-cyclohexane (1.33 mmol). After the addition of 10 ml H2 via syringe 17.7% conversion of 1-methylcyclohexane to methylcyclohexane was observed in the 1H-NMR spectrum after 5 minutes. In 1 hour, 52.4% conversion of 1-methylcyclohexane to methylcyclohexane was observed in the 1H-NMR spectrum (15 ml extra H2 was added via syringe).

Comparative Example (C) A solution of 10 mg [Cp (nBu)] 2ZrMe2 (27.5 μmol) in 0.5 g of benzene-d6 was mixed with 1.6 g of a solution of methylalumoxane in toluene. An NMR tube was loaded with one third of this mixture and 120 mg of 1-methyl-cyclohexane (1.25 mmol) was added. After the addition of 10 ml H2 via syringe, conversion of 1-methylcyclohexane to methylcyclohexane in the 1H-NMR spectrum after 2 hours was not observed.

It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is that which is clear from the manufacture of the objects to which it refers. Having described the invention as above, the content of the following is claimed as property.

Claims (12)

1. A catalyst composition which comprises at least: a) a metal compound cation of the formula [(A) (B) ML +] wherein M represents titanium, zirconium, or hafnium, wherein A and B represent binders with the Structure I or II. Structure I structure II characterized in that Ri independently represents the same or different hydrocarbyl groups optionally containing heteroatoms, and R3 independently represents the same or different hydrocarbyl groups that optionally contain heteroatoms, or a halide, and in which the substituent atoms R may be options between A and B to provide a bridge, where m is an integer from 0-5, p is an integer from 0-4, and q is an integer from 0-3, where L represents the group hydrogen or hydrocarbyl optionally containing heteroatoms, with the proviso that if A and B are both binders with structure I or II, at least one m, poq is at least 1, and b) a different stable anion.

2. A catalyst composition according to claim 1, characterized in that the metal compound cation has the structure III [lRc22 M "structure III where M = titanium or zirconium, where A = a binder with structure I or II in which Ri and R2 are independently the same or different hydrocarbyls that optionally contain a heteroatom, and R3 is a hydrocarbyl optionally containing a heteroatom, or a halide; R2 can be combined with Ri or R3 to form a bridge; where m is an integer from 0-5, p is an integer of 0-4, and q is an integer of 0-3, and n is an integer of 1-5; wherein L represents the hydrocarbyl group or hydrogen optionally containing heteroatoms.

3. Catalyst compositions according to claim 2, characterized in that R2 is a branched hydrocarbyl of 3 to 15 carbon atoms and optionally contains heteroatoms.

4. Catalyst compositions according to claim 3, characterized in that R2 is a tertiary butylyl trimethylsilyl.

5. Catalyst composition according to any of claims 1-4 characterized in that the different anion has the formula [RB (Ar) 3_] where Ar represents a hydrocarbyl group that strongly extracts an electron; wherein R is Ar, hydride, or a hydrocarbyl group optionally containing heteroatoms.

6. Catalyst compositions according to claim 5, characterized in that Ar is C6F5 or 3.5- (CF3) 2C6H3.

7. A catalyst composition according to claim 1, obtained by reacting a metal compound of formula (A) (B) ML2, characterized in that A, B, M and L are as defined in claim 1, with a salt of a different stable anion.

8. A catalyst composition according to claim 7, characterized in that the salt of the different stable anion is D + [B (Ar) 4] "0 B (Ar) 3 wherein Ar is a hydrocarbyl strongly separated from the electron and D is a cation capable of reacting with an L of the metal compound from a DL compound.

9. A process for the preparation of a catalyst composition which comprises reacting a) a metal compound of the formula (A) (B) ML2 wherein M represents titanium, zirconium, or hafnium, wherein A and B represent binders with Structure I 'or II. Structure I structure II characterized in that Ri independently represents the same or different hydrocarbyl groups optionally containing heteroatoms, and R3 independently represent the same or different hydrocarbyl groups that optionally contain heteroatoms, or a halide, and in which the substituent atoms R may be options between A and B to provide a bridge, where m is an integer from 0-5, p is an integer of 0-4, and q is an integer of 0-3, where L represents the group hydrogen or hydrocarbyl which optionally contain heteroatoms, with the proviso that if A and B are both binders with structure I and II, at least one of m, poq is at least 1, with b) a salt of a stable anion different or non-coordinating.

10. A process for the hydrogenation of olefins or oligomers, polymers or copolymers characterized by containing unsaturated ethylenic compounds, using hydrogenation catalyst compositions according to any of claims 1-8.

11. A process for the hydrogenation of homopolymers of conjugated dienes or blocks of copolymers, characterized in that they have at least one poly (monovinylaromatic) block and at least one block poly (linear or branched conjugated dienes), using catalyst compositions for hydrogenation , in accordance with any of claims 1-8.

12. A method according to claim 11, characterized in that the catalyst composition is present in a concentration such as

0. 1 to 0.75 g of group 4 of metals is present per 100 grams of the polymer. SUMMARY OF THE INVENTION Catalysts and Procedures for the Hydrogenation of Olefins or Polymers The present invention relates to catalyst compositions which comprise at least: a) a metal compound cation of the formula [(A) (B) ML +] wherein M represents titanium, zirconium, or hafnium, wherein A and B represent binders with structure I or II. Structure I structure II in which Ri independently represents the same or different hydrocarbyl groups optionally containing heteroatoms, and R3 independently represent the same or different hydrocarbyl groups that optionally contain heteroatoms, or a halide, and in which the R substituents may be options between A and B to provide a bridge, where m is an integer from 0-5, p is an integer of 0-4, and q is an integer of 0-3, where L represents the group hydrogen or hydrocarbyl optionally containing heteroatoms, with the proviso that if A and B are both ligands with structure I and II, at least one of m, poq is at least 1, and b) a different stable anion. The present invention further relates to a process for the preparation of a catalyst composition and to a process for the catalytic hydrogenation of olefins, oligomers, polymers or copolymers.