MXPA01000918A - Unbridged monocyclopentadienyl metal complex catalyst having improved tolerance of modified methylaluminoxane - Google Patents

Abstract

There is provided a catalyst containing a transition metal precursor having the formula (C5R15)TiY3, (wherein each y is independently selected from the group consisting of a C1-C20 alkoxide, a C1-C20 amide, a C1-C20 carboxylate and a C1-C20 carbomate) an alcohol or carboxylic acid, an aluminoxane, and optionally a substituted bulky phenol and/or a support or spray drying material. There is also provided a polymerization process employing the catalyst composition, a polymer produced using the catalyst, and a cable produced therefrom.

Description

CATALYST METAL COMPLEX MONOCICLOPENTADIENILO WITHOUT BRIDGE THAT HAS BETTER TOLERANCE OF METILALUMINOXANO MODIFIED FIELD OF THE INVENTION The invention relates to a catalyst composition for polymerization of olefins and to a process for the polymerization of polyolefins, especially copolymers of ethylene alpha-olefins, ethylene alpha-olefin dienes, and polypropylene using a metallocene catalyst. More particularly, the invention addresses the polymerization of polyolefins having less than 50% crystallinity using a metallocene catalyst containing a transition metal and an aluminoxane.

BACKGROUND OF THE INVENTION There has been increasing interest in the use of metallocenes in the production of polyolefins. Many metallocenes for the production of polyolefins are difficult to prepare and consume time, require large amounts of alumoxane, and show little reactivity with respect to higher olefins, especially for preparing ethylene alpha-olefin copolymers and ethylene alpha-olefin diene terpolymers. In addition, ethylene alpha-olefin copolymers, and ethylene alpha-olefin diene terpolymers prepared using these metallocenes often have low unwanted molecular weights (ie, Pm less than 50,000). The so-called "forced geometry" catalysts such as those described in EP 0 420 436 and EP 0 416 815 can provide a greater response to the comonomers and a higher molecular weight copolymer, but their preparation and purification is difficult, and so They are so expensive. Another disadvantage of the catalyst system with amido-cyclopentadienyl titanium bridge is that to form a catalyst with active oxide support, it is necessary to definitely use higher levels of alumoxane (see, for example, WO 96/16092) or to use mixtures of alkylaluminium and an activator a base of tris (pentafluorophenyl) borane derivatives (see, for example, WO 95/07942), itself an expensive reagent, in this way, raising the cost of running the catalyst. In the technique of forced geometry catalysts, such as in EP 0 416 815 A2 (page 2, lines 5-9 and 43-51), it is pointed out that the angle formed by the cyclopentadienyl centroid, the transition metal and nitrogen of the amide is critical for the operation of the catalyst. Indeed, the comparison of the published result using amidocyclopentadienyl titanium systems with bridging and similar systems without bridging, in general shows that the unbridged analogues are relatively inactive. Such a system, described in U.S. Patent No. 5,625,016, shows very low activity, while having some of the desirable behavior of the copolymerization. In Idemitsu Kosan JPO 8/231622, it was reported that the active catalyst can be formed from (C5Me5) Ti (OMe) 3 ^ and that the polymer formed has a relatively broad or extensive compositional distribution.

The present invention does not use this precursor. Typically, polyolefins such as EPR and EPDM are commercially produced using vanadium catalysts. In contrast to other polyolefins produced using vanadium catalysts, those produced by the catalysts of the present invention have higher molecular weight and narrower composition distribution (i.e., lower crystallinity at an equivalent alpha-olefin content). Presently it is a need to provide a catalyst employing a metallocene which is easy to prepare, does not require large amounts of aluminoxane and which rapidly copolymerizes to produce ethylene alpha-olefin copolymers, ethylene alpha-olefin diene terpolymers, and polypropylene, as well as to produce polyethylene.

COMPENDIUM OF THE INVENTION In contrast to the forced geometry catalysts, the catalyst of the present invention is non-forced or bridged and relatively easy and inexpensive to prepare using commercially available raw materials. further, the level of aluminoxane used can be decreased. That is, in the present invention, the precursor can be dried on a support or dried with a material for spray drying with Al: Ti ratios below 100: 1 to form more active catalysts with polymerization behavior similar to analogs without support of the invention and similar polymerization behavior with the forced catalysts. In addition, the catalysts of the present invention described herein have better reactivity with methylaluminoxane (MMAO) containing higher alkyl groups. This facilitates the replacement of some or all of the toluene used in the polymerization medium with light aliphatic hydrocarbons, since MMAO, unlike aluminoxane (MAO), is soluble in non-aromatic solvents. The use of aliphatic hydrocarbons such as isopentane is often preferred to toluene because of the greater ease of purging it from the polymer after it leaves the reactor and also because of the adverse health aspects associated with aromatic solvents in general. Accordingly, the present invention provides a catalyst comprising: (A) a transition metal compound having the formula: (C5R15) TiY3, wherein each substituent R1 is independently selected from the group consisting of hydrogen, C? C8, an aryl and an alkyl or aryl substituted with heteroatom, with the proviso that not more than three substituents R1 are hydrogen; and wherein two or more R1 substituents can be linked together to form a ring; and each Y is independently selected from the group consisting of a C? -C20 alkoxide, C? -C20 amide, C1-C20 carboxylate, and a C1-C20 carbamate; (B) a compound having the formula: R2OH or R3COOH, wherein each R2 or R3 is a Ci-Cß alkyl; and (C) an aluminoxane. Optionally, the catalyst may additionally contain (D) a bulky phenol compound having the formula: (C6R45) OH, wherein each R4 group is independently selected from the group consisting of hydrogen, halide, a C? -C8 alkyl, a aryl, an alkyl or aryl substituted with heteroatom, wherein two or more R4 groups may be linked together to form a ring, wherein at least one R4 is represented by a linear or branched C3-C12 alkyl located on either or both positions 2 and 6 (ie, the ortho positions relative to the OH groups being in the 1-position) of the bulky phenol compound. A polymerization process that employs the catalyst composition and a polymer produced using the catalyst is also provided. A composition for cable is also provided.

DETAILED DESCRIPTION OF THE INVENTION Catalyst. The catalyst contains a precursor (Component A) of transition metal (titanium), an alcohol or carboxylic acid (Component B), an aluminoxane (Component C), and optionally a bulky substituted phenol (Component D). The catalyst of the invention can be unsupported (ie, in liquid form), supported, spray dried, or used as a prepolymer. The support and / or spray-drying material is described as the optional Component E. Component A. A transition metal compound (A) having the formula: (CsR ^) TiX3, wherein each substituent R1 is independently selected from the group consisting of hydrogen, C?-C8 alkyl, an aryl, and a aryl or alkyl substituted with heteroatom, with the proviso that not more than three substituents R1 are hydrogen; and wherein two or more substituents R1 may be linked together to form a ring; and each Y is independently selected from the group consisting of C? -C20 alkoxide, an C? -C20 amide, a C? -C2o carboxylate and a carbamate C1-C20- Illustrative compounds may include: cyclopentadienyltitanium tribenzoate; cyclopentadienyltitanium tris (diethylcarbamate); cyclopentadienyltitanium tris (di-tert-butylamide); cyclopentadienyltitanium tripenoxide; pentamethylcyclopentadienyltitanium tribenzoate; pentamethylcyclopentadienyltitanium tri-pivalate; pentamethylcyclopentadienyltitanium triacetate; pentamethylcyclopentadienyltitanium tris (diethylcarbamate); pentamethylcyclopentadienyltitanium tris (di-tert-butylamide); pentamethylcyclopentadienyltitanium tripenoxide; 1,3-bis (trimethylsilyl) cyclopentadienyltitanium tribenzoate; tetramethylcyclopentadienyltitanium tribenzoate; fluoreniltitanium trichloride; 4,5,6,7-tetrahydroindeniltitanium tribenzoate; 4,5,6,7-tetrahydroindeniltitanium tripivalate; 1,2,3,4,5,6,7,8-octahydrofluoreniltitanium tribenzoate; 1,2,3,4,5,6,7,8-octahydrofluoreniltitanium tris (diethylcarbamate); 1,2,3,4-tetrahydrofluoreniltitanium tribenzoate; 1,2,3,4-tetrahydrofluorenyl-titanium tris (di-tert-butylamide); 1,2,3-trimethylcyclopentadienyltitanium tributyrate; 1,2,4-trimethylcyclopentadienyltitanium tribenzoate; 1, 2, -trimethylcyclopentadienyltitanium triacetate; l-n-butyl-3-methylcyclopentadienyltitanium tribenzoate; 1-n-butyl-3-methylcyclopentadienyltitanium tripi alato; methylindeniltitanium tripropionate; 2-methylindenititanium tribenzoate; 2-methylindeniltitanium tris (di-n-butylcarbamate); 2-methylindeniltitanium tripenoxide; and 4,5,6,7-tetrahydro-2-methylindenititanium tribenzoate. In the precursor, a heteroatom is an atom other than carbon (eg oxygen, nitrogen, sulfur, etc.) in the ring of the heterocyclic fraction. Component B is an alcohol having the formula: R20H or R3COOH, wherein each R2 or R3 is a C? -C8 alkyl. Illustrative compounds R20H wherein R2 is alkyl may include, for example, methanol, ethanol, propanol, butanol (including n- and t-butanol), pentanol, hexanol, heptanol, octanol. Preferably, R2 is a methyl group. Illustrative R3COOH compounds are acetic acid, propionic acid, benzoic acid and pivalic acid. Preferred among these are benzoic acid and pivalic acid. Component C is a co-catalyst capable of activating the catalyst precursor which is used as component D. Preferably, the activating co-catalyst is a linear or cyclic oligomeric poly (hydroxycarbonylaluminum) oxide containing repeated units of the general formula - (A1 (R *) 0) -, where R * is hydrogen, an alkyl radical containing from 1 to 12 carbon atoms, or an aryl radical such as a substituted or unsubstituted phenyl or naphthyl group. More preferably, the activating cocatalyst is an aluminoxane such as methylaluminoxane (MAO) or modified methylaluminoxane (MMAO).

Aluminoxanes are well known in the art and comprise linear oligomeric alkyl aluminoxanes, represented by the formula: and cyclic oligomeric alkyl aluminoxanes of the formula: wherein s_ is 1-40, preferably 10-20; £ > it is 3-40, preferably 3-20; and R *** is an alkyl group containing 1 to 12 carbon atoms,. preferably methyl. Aluminoxanes can be prepared in a variety of ways. Generally, a mixture of cyclic and linear aluminoxanes is obtained in the preparation of aluminoxanes from, for example, trimethylaluminum and water. For example, an aluminum alkyl can be treated with water in the form of a wet solvent. Alternatively, an aluminum alkyl, such as trimethylaluminum, may be contacted with a hydrated salt, such as ferrous sulfate hydrate. The latter method comprises treating a dilute solution of dimethylaluminum in, for example, toluene with a suspension of ferrous sulfate heptahydrate. It is also possible to form methylaluminoxanes by the reaction of a tetraalkyldialuminoxane containing C2 or higher alkyl groups with an amount of trimethylaluminum which is less than a stoichiometric excess. The synthesis of methylaluminoxanes can also be carried out by reacting a trialkylaluminum compound or a tetraalkyldialuminoxane containing C2 or higher alkyl groups with water to form a polyalkylaluminoxane, which is then reacted with dimethylaluminum. In addition, the modified methylaluminoxanes, which contain methyl groups and higher alkyl groups, i.e. isobutyl groups, can be synthesized by the reaction of a polyalkylaluminoxane containing C2 or higher alkyl groups with trimethylaluminum and then with water as described in, for example. , U.S. Patent No. 5,041,584. The molar ratio of aluminum atoms contained in the poly (hydrocarbyl aluminum oxide) to the total atoms contained in the catalyst precursor is generally in the range from about 2: 1 to about 10,000: 1, preferably in the range from about 10: 1 to about 10,000: 1, and more preferably in the range from about 50: 1 to about 2,000: 1. Preferably, component C is an alumoxane of the formula (A1R50) m (A1R60) n in which R5 is a methyl group, R6 is an alkyl of Ci-Cs, m ranges from 3 to 50; and n ranges from 1 to 20. More preferably, R6 is a methyl group. Component D is optional and is a bulky phenol compound having the formula: (C6R45) OH, wherein each R4 group is independently selected from the group consisting of hydrogen, halide, Ci-Cg alkyl, an aryl, an aryl or alkyl substituted with heteroatom, wherein two or more R4 groups may be linked together to form a ring, and in which at least one R4 is represented by a linear or branched C3-C12 alkyl located in either or both of the 2 and 6 positions (ie, the ortho positions relative to the OH group being in the 1-position) of the bulky phenol compound. In the formula, preferably none of the R4 groups is a methoxy group. Preferably, suitable groups R4 may include, for example t-butyl, isopropyl, n-hexyl and mixtures thereof. Component E. Preferably, the catalyst of the invention is unsupported. However, optionally one or more of the catalyst components described above may be impregnated or deposited on a support, or alternatively spray-dried with a support material. These supports or materials for spray drying are normally solid materials which are inert with respect to the other components of the catalyst and / or reactants used in the polymerization process. Suitable spray drying support or materials may include silica, carbon black, polyethylene, polycarbonate, cross-linked porous polystyrene, cross-linked porous polypropylene, alumina, thoria, titania, zirconia, magnesium halide (eg, magnesium dichloride), and mixtures thereof. Among these preferred support materials are silica, alumina, carbon black, and mixtures thereof. These are composed of particularly porous supports that have usually been calcined at a temperature sufficient to remove substantially all physically bound water. The molar ratio of Component B to Component A ranges from about 2: 1 to 200: 1, preferably about 2: 1 to 50: 1.; and, more preferably, it is about 2: 1 to 20: 1. The molar ratio of component D for component A ranges from about 5: 1 to 1000: 1; preferably about 10: 1 to 300: 1; and, more preferably, about 30: 1 to 200: 1. The molar ratio of Component C for Component A ranges from about 10: 1 to 10,000: 1, preferably about 30: 1 to 2,000: 1, and more preferably is about 50: 1 to 1000: 1, with the conditions of that: (1) the ratio of Component B for Component C does not exceed 0.7: 1, and is preferably between 0.001: 1 to 0.050: 1; and (2) the ratio of Component B for Component C does not exceed 1: 1, and is preferably less than 0.7: 1. When Component E is used as a support or spray-drying material, it is used in an amount ranging from about 7 to 200 g / mmol, preferably from 12 to 100 g / mmol, and more preferably from 20 to 70 g / mmol (grams of Component E per millimole of Component A).

Process to prepare the catalyst. The individual catalyst components (Components A, B, C and optionally D and E) can be combined in any order before polymerization. Alternatively, the individual catalyst components can be fed to the polymerization reactor so that the catalyst is formed in situ. Preferably, the active catalyst is prepared as follows. In step 1, Components A and B are mixed in a suitable inert hydrocarbon solvent to dissolve components A to C, and optionally also D under an inert atmosphere (eg nitrogen) for at least 15 minutes or more (eg, up to 3 days). The components are combined so that Component A is mixed with at least three molar equivalents of Component B. Common inert solvents may include, for example, toluene, xylene, chlorobenzene, etc. Among these preferred solvents is toluene. In step 2, Component C (or Component C and Component D, when employed) are mixed in one of the inert hydrocarbon solvents described above, preferably the same solvent used in step 1, under an inert atmosphere (e.g. , nitrogen and / or argon) for at least 15 minutes or more (for example, up to 3 days). The ratio of aluminum (in the aluminoxane, Component C) to phenol of the bulky phenol compound (Component D) ranges from 1.4: 1 to 1000: 1; preferably 3: 1 to 100: 1; more preferably 3: 1 to 10: 1. Optionally, the support or spray drying material (Component E) can be added to any of the solutions, mixtures and / or slurries described above. When the component E is used, the mixing should take place for about 30 minutes or more and the aluminum ratio for the support material will be in the range from about 0.5 to 10 mmol / g, preferably 2 to 5 mmol / g. In step 3, the mixture of Components A and B is combined with the mixture of Components C (or Component C and D, when D is used) (and optionally E) in such proportion that the molar ratio of aluminum to the metal of transition is about 5 to 5000, preferably 30 to 1000, and the molar ratio of Component B to aluminum is less than 0.5. The mixture is stirred for at least about 5 minutes. The mixture can be used as a liquid for direct injection in the polymerization reactor, or if Component E is present, it can be dried under vacuum to a free-flowing or spray-dried powder in an inert atmosphere. If Component E is not present, the catalyst is then fed to the reactor in liquid form. If Component E is present and the catalyst is in solid form, they can be introduced into the reactor by a variety of methods known to those skilled in the art, such as by inert gas transport or by injection into a catalyst slurry with mineral oil. . Although we do not wish to be bound by any theory, it is believed that the function of the two protic reagents (Components B and C) is to prevent the degradation of the active sites of cationic (IV) titanium. It is known that trialkyl aluminum compounds (A1R3) are rapidly reduced to the oxidation state of titanium from +4 to +3. However, it is usually advantageous to have A1R3 or aluminoxanes present during the polymerization to serve as catalyst scavengers of catalysts that adhere to the surfaces of the reactor or are introduced by the reaction medium such as monomers, inert gases, and (if appropriate) ) solvents. Therefore, the catalyst of the invention represents a solution to the problem of titanium reduction that allows the presence of alkylaluminium species. It has been postulated that the first step in the activation of titanium by co-catalysts is alkylation, that is, the exchange of two or more titanium substituents with alkyl groups in atom (s) of aluminum. So the reason that catalysts based on titanium carboxylates are more active than their trihalide analogs under certain polymerization conditions (notable for EPDM polymerization) is that the aluminum carboxylates that are formed immediately from the alkylation reaction of the tricarboxylates serve as bulky groups. It is believed that these bulky groups prevent a close interaction of the aluminum species with the species of alkylated titanium, thus hampering the reduction and complexing reactions.

Process and polymerization conditions. The composition of the catalysts described above can be used for the polymerization of monomers (for example olefins, diolefins and / or vinyl aromatics) in a slurry, solution, slurry, or gas phase process using known equipment and reaction conditions, and this is not limited to any specific type of reaction. However, the preferred polymerization process is a gas phase process using a fluidized bed. The gas fluidized bed reactor can be assisted by mechanical agitation or agitation means. The gas phase process that is employed in the present invention may include gas phase processes also called "conventional" "condensed mode", and more recent processes "in liquid mode". In many processes, it is desirable to include a scrubber in the reactor to remove foreign poisons such as water or oxygen, before these can decrease catalyst activity. In such cases, it is recommended that trialkylaluminium species (eg, TIBA) be not used, but preferably that methylalumoxane be used for such purposes. Conventional fluidized processes are described, for example, in U.S. Patent No. 3,922,322; 4,035,560; 4,994,534 and 5,317,036.

Condensed mode polymerizations, including induced condensate mode, are taught, for example, in U.S. Patent Nos. 4,543,399; 4,588,790; 4,994,534; 5,317,036; 5,352,749 and 5,462,999. For polymerizations that produce copolymers and homopolymers of alpha olefins, the mode of operation by condensation is preferred. The manner of polymerization of liquid monomer or liquid mode is described in U.S. Patent No. 4,453,471; American Series No. 510,375; and WO 96/04322 (PCT / US95 / 09826) and WO 96/04323 (PCT / US95 / 09827). In the liquid monomer or liquid mode polymerizations the temperature in the polymerization zone of the reaction vessel is maintained below the dew point of at least one of the monomers used. The fluidization is achieved by a high rate of recycling of the fluid to and through the bed, regularly in the order of approximately 50 times the feed rate of the fluid constituted. The fluidized bed has the general appearance of a dense mass of individually moving particles created thus by the infiltration of gas through the bed. For polymerizations such as ethylene-propylene copolymer (e.g. EPM), ethylene-propylene-diene terpolymer (e.g. EPDM), and diolefin polymerizations (e.g., butadiene, isoprene), it is preferable to use the liquid mode and employ an inert particulate material. , a so-called fluidization aid. Inert particulate materials are described, for example, in U.S. Patent No. 4,994,534 and include carbon black, silica, clay, talc, and mixtures thereof. Of these, carbon blacks, silica and mixtures thereof are preferred. When used as fluidization aids, these inert particulate materials are used in amounts ranging from about 0.3 to about 80% by weight, preferably about 5 to 50% based on the weight of the polymer produced. The use of inert particulate materials as fluidization aids in the polymerization of the polymer produces a polymer having a core-shell configuration as described in U.S. Patent No. 5,304,588. The catalyst of the invention, in combination with one or more of these fluidization aids, produces a resin particle comprising an outer shell having a mixture of a polymer and an inert particulate material, wherein the inert particulate material is present in the outer shell in an amount greater than 75% by weight, based on the weight of the outer shell; and an inner core having a mixture of inert particulate material and polymer, wherein the polymer is present in the inner core in an amount greater than 90% by weight, based on the weight of the inner core. In the case of polymers # sticky, these resin particles are produced by fluidized bed polymerization processes at or above the softening point of the sticky polymer. Polymerizations can be carried out in a single reactor or multiple reactors, usually two or more connected in series, can also be employed. The essential parts of the reactor are the vessel, the bed, the gas distributor plate, the inlet and outlet pipe, at least one compressor, at least one cycle gas cooler, and a product discharge system. In the vessel, above the bed, there is a zone of speed reduction, and in the bed a reaction zone. In general, all the above-mentioned polymerization methods are carried out in a gas-phase fluidized bed with a "seed bed" of polymer that is the same or different from the polymer being produced. Preferably, the bed is made up of the same granular resin that is produced in the reactor. The bed is fluidized using a fluidizing gas consisting of the monomer or monomers being polymerized, initial feed, feed refill, cycle gas (recycled), inert carrier gas (eg, nitrogen, argon or inert hydrocarbon such as methane, ethane, propane, isopentane) and, if desired, modifiers (e.g., hydrogen). From < this way, during the course of an I! polymerization, the bed comprises polymer particles I formed, particles of polymer in growth, particles of catalyst, and optionally flux auxiliaries.

Gas-phase reactor are such that the temperature can vary from sub-atmospheric to super-atmospheric, but it is commonly from about 0 to 120 ° C, preferably about 40 to 100 ° C, and more preferably about 40 to 100 ° C. up to 80 ° C. The partial pressure i will vary depending only on the particular monomer or monomers used and the temperature of the polymerization, and this can vary from about 1 to 300 psi (6.89 to 2.0067 kilopascals), preferably 1 to 100 psi (6.89 to 689 kilopascals). The condensation temperatures of the monomers such as butadiene, isoprene, styrene are well known. In general, it is preferred to operate at a partial pressure slightly above or slightly below the dew point of the monomer (i.e., for example, ± 10 ° C for low-boiling point monomers). Polymers produced. The olefin polymers that • can be produced according to the invention include, but are not limited to, ethylene homopolymers, linear or branched higher alpha-olefin homopolymers containing from 3 to about 20 carbon atoms, and interpolymers of ethylene and such alpha olefins higher, with densities ranging from about 0.84 to about 0.96. The homopolymers ^^ 10 and propylene copolymers can also be produced by the catalyst and inventive process. Suitable higher alpha-olefins include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 3,5,5-trimethyl-1-hexene. Preferably, the olefin polymers according to the invention may also be based on or contain non-conjugated dienes or conjugates such as linear, branched hydrocarbon dienes of cyclics having from about 4 to about 20, preferably 4 to 12. , carbon atoms. The preferred 20 dienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbornene, 1,7-octadiene, 7-methyl-1, 6-octadiene, vinyl cyclohexene, dicyclopentadiene, butadiene, isobutylene, isoprene, ethylidene norbornene, and the like. Aromatic compounds having vinyl unsaturation such as styrene and substituted styrenes, and polar vinyl monomers such as acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters, methacrylate esters, vinyl trialkyl silanes and the like can be polymerized according to the invention as well. The 1 specific olefin polymers that can be made according to the invention include, for example, polyethylene, polypropylene, ethylene / propylene rubbers (EPR), ethylene / propylene / diene terpolymers (EPDM), polybutadiene, pplisoprene and the like. The present invention provides a cost effective catalyst and method for preparing high molecular weight ethylene alpha olefins copolymers, homogeneous in composition with very high levels of alpha olefin. An advantage is that the catalyst has a very high response to the comonomers, so that the ratio of the alpha olefin to the ethylene present in the reaction medium can be very low, which increases the partial pressure of the possible ethylene in the reactor . This improves catalyst activity. It also decreases the level of residual comonomer that must be purged or otherwise recovered from the polymer after it leaves the reactor. The catalyst is also suitable for the incorporation of non-conjugated dienes to form elastomeric compositions or completely amorphous rubber. The very high response to the catalyst comonomers also makes it a good candidate for the incorporation of branched long chains in the polymer architecture through the insertion of vinyl-terminated polymer chains formed by the removal of β-hydride. The ethylene copolymers produced by the present invention have polydispersity values (PDI) ranging from 2 to 4.6, preferably 2.6 to 4.2. The polymers produced using the catalyst and / or the process of the invention have utility in wire and cable applications, as well as in other articles, such as molded and extruded articles, hoses, transmission belts, roofing materials, tire components ( rim, side face, inner lining, casing, belt). The polyolefins produced using the catalyst and / or process of the invention can be cross-linked, vulcanized or cured using techniques known to those skilled in the art. In particle.r, there is provided by the invention a cable comprising, each one, one or more electrical conductors, or a core of electric conductors, surrounded by an insulating composition consisting of a polymer produced in a gas phase polymerization process using the catalyst of the invention. Preferably, the polymer is polyethylene; a copolymer of ethylene, one or more alpha olefins having 3 to 12 carbon atoms, and optionally, d or n (s) Conventional additives, which can be introduced into the cable and / or polymer formulation, are exemplified by antioxidant: is, coupling agents, ultraviolet light absorbers or stabilizers, antistatic agents, pigments, dyes, nucleating agents, reinforcing fillers or polymeric additives, slip agents, plasticizers, processing aids, lubricants, viscosity controlling agents, binders, antiblocking agents, surfactants, rubber extender oils, metal deactivators, voltage stabilizers, flame retardant fillers, and additives, cross-linking agents, re-formers and catalysts, and smoke suppressants. The fillers and additives may be added in amounts ranging from less than about 0.1 to more than about 200 parts by weight per 100 parts by weight based on the resin, for example polyethylene. Examples of antioxidants are: hindered phenols such as tetrakis [methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate)] -methane, bis [(beta- (3, 5-di-tert-butyl-4- hydroxybenzyl) -methylcarboxyethyl)] sulfide, 4,4'-thiobis (2-methyl-6-tert-butylphenol), 4, '-thio-bis (2-tert-butyl-5-methylphenol), 2,2' - thiobis (4-methyl-6-tert-butyl-phenol), and thiodiethylene ois (3,5-di-tert-butyl-4-hydroxy) hydrocinnamate;phosphites and phosphonites such as tris (2,4-di-tert-butyl-phenyl) phosphite and di-tert-butylphenyl-phosphonite; thio compounds such as dilaurylthiopropionate, dimyristylthiodipropionate and distearylthiodipropionate; some siloxanos; and some amines such as polymerized 2,2,4-trimethyl-1,2-dih: .droquinoline. Antioxidants that can be used in amounts from about 0.1 to about 5 parts by weight per 100 parts by weight of polyethylene. The resin can be crosslinked by adding a crosslinking agent to the composition or making the resin hydrolyzable, which is achieved by the addition of hydrolyzable groups such as -Si (OR) 3, wherein R is a hydrocarbyl radical, the structure of the resin by copolymerization or grafting. Suitable crosslinking agents are organic peroxides such as dicumyl peroxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; t-butylcumyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3. Dicumyl peroxide is preferred. The hydrolysable groups can be added, for example, by copolymerization of ethylene with an ethylenically unsaturated compound having one or more -Si (OR) 3 groups such as vinyltrimethoxy-silane, vinyltriethoxysilane and gamma-methacryloxypropyltrimethoxysilane or by grafting these silanb compounds to the resin in the presence of the organic peroxides previously mentioned. The hydrolysable resins are then crosslinked by moisture in the presence of a silanol condensation catalyst such as dibutyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, stannous acetate, lead naphthenate and zinc caprylate. Dibutyltin dilaurate is preferred. | Examples of hydrolysable copolymers and hydrolysable graft copolymers are ethylene / vinyltrimethoxysilane copolymer, ethylene / gamma-methacryloxypropyltrimethoxysilane copolymer, ethylene vinyltrimethoxysilane copolymer grafted with ethyl acrylate, linear grafted low density ethylene copolymer I with vinyltrimethoxysilane / 1-butene and low density polyethylene grafted with vinyltrimethoxysilane. The cable and / or the polymer formulation may contain a polyethylene glycol (PEG) as taught in EP 0 735 545. The cable of the invention can be prepared in various types of extrusions, for example, single or double type. propellers. The composition can be made in the extruder or prior to extrusion in a mixer in conventional manner I such as Brabender ™ mixer or Banbury ™ mixer. A description of a conventional extruder can be found in i U.S. Patent No. 4,857,600. A typical extruder has a hopper at its upper end portion and a nozzle at its downstream end portion. The hopper feeds a drum containing a propeller propeller. To the extreme • Downstream, between the end of the propeller propeller and the nozzle, is a packed sieve and a breaker plate. 5 The propeller propeller portion of the extruder is considered to be divided into three sections, the feeding section, the compression section and the introduction section and two zones, the hot zone of the rear part and the hot zone of the front part, the ^^ 10 sections and areas run from top to bottom. In the alternative, there may be multiple heating zones (more than two) along the axis running from top to bottom. If you have more than one drum, the drums are connected in series. The length to diameter ratio of each drum is in the range of about 15: 1 to about 30: 1. In the wire coating, where the material is crosslinked after extrusion, the ^ P nozzle of the crosshead feeds directly into a heating zone, and this zone can be maintained at a temperature in the range of about 130 ° C to about 260 ° C, and preferably in the range of about 170 ° C to about 220 ° C. All references cited here are incorporated by reference. Although the scope of the invention is apparent in the accompanying clauses, the following specific examples illustrate certain aspects of the present invention. The examples are indicated as illustration only and should not be considered as limitations of the invention, except as stated in the clauses. All parts and percentages are by weight unless otherwise specified.

Examples Glossary and abbreviations: DSC: differential scanning calorimetry DTBP: 2,6-di-t-butylphenol ENB: 5-ethylidene-2-norbornene Fl: flow index, ASTM standard 121, in dg / min ICP: plasma method inductively coupled for elemental analysis Irganox Irganox® 1076, a product of Ciba-Geigy Kemamine Kemamine® AS-990, a product of Witco Corp. MAO: methylalumoxane (Ethyl / Albemarle, solution in toluene, 1.8 or 3.6 moles Al / L) MMAO : modified methylalumoxane (Akzo Nobel) PDI: polydispersity index or Mw / Mn PRT: maximum recrystallization temperature, the exothermic peak of the cooling fingerprint in a DSC SEC experiment: size exclusion chromatography method for molecular weight estimation TIBA: triisobutylaluminum, 0.87 mol / l in hexanes Materials Pentamethyl cyclopentadienyl titanium trichloride and indeniltitanium trichloride were obtained from Stre Chemicals Inc., and used without further purification, Examples 1-5 These examples show the use of the catalyst of this invention to copolymerize ethylene and 1-hexene. In these examples, toluene was first dried by absorption on anhydrous MgSO4 for at least 7 days, followed by filtration through paper, spraying with nitrogen, stored on addition of sodium / potassium, for at least 24 hours and filtration through of dry alumina. In this way dried, it was stored in a dry box under nitrogen.

Example 1 Preparation of (C5Me5) Ti (? 2CPh) 3 All manipulations were carried out under a nitrogen atmosphere. A Schlenk flask was charged with a stir bar, 25 ml of anhydrous toluene and 2.01 g (C5Me5) TiCl3 (6.94 mmol). 3.37 g of benzoic acid (27.6 mmol) and the stirring bar were placed, and the solution of (C5Me5) TiCl3 was transferred to it by cannula. To the resulting orange mixture were added 2.9 ml (20.7 mmol) of triethylamine, and the solution was allowed to stir at room temperature for three hours and then filtered. The solid was washed with toluene, leaving it colorless. The filtrate was reduced in vacuo to approximately 10 ml, then maintained at 21 ° C per ca. 5 hours. The sample was then filtered and washed with cold toluene, and briefly dried by flowing nitrogen through the filtrate cake, leaving an orange yellow solid, 0.747 g. The 1H nmr spectrum revealed the presence of residual solvent and benzoic acid. The latter was estimated to be 0.83 molar equivalents per titanium atom. After subtracting the benzoic acid contributions, the main rmn peaks for the titanium complex are as follows (d, solvent CD2C12): (XH rmn) 7.97 (2H, d, J = 7.14 Hz), 7.52 (HH, m) , 7.40 (2H, t, J = 7.5 Hz), 2.12 (15H, s); "C ^ HJrmn) 133.1, 129.2, 128.6, 11.8 A solution of (C5Me5) Ti (02CPh) 3 in toluene containing 0.83 eq of benzoic acid (0.025 g in 5 ml, 7.7 mmol Ti / L) was prepared under A mixture composed of 1 ml of the above solution and 0.32 ml of a solution of methanol in toluene (0.123 mol / l, 0.039 mmol MeOH, MeOH / Ti = 5.1) was prepared and stirred for 40 min at room temperature. A 1.3 1 stainless steel reactor (Fluitron®), dried by nitrogen stream while being maintained at 100 ° C for at least one hour (h) was cooled, then charged with 650 ml hexane, 40 ml 1-hexene, 0.69 ml MAO (1.8 mol / 1 in toluene, 1.24 mmol Al) and 1.4 ml of a solution of DTBP in toluene (0.182 mol / 1, 0.025 mmol, Al / DTBP = 5.0) The reactor had two inserted mobile derailleurs and one impeller In the form of a variable speed propeller, which was run at 800 rpm, the reactor was heated to 40 ° C and ventilated to release most of the nitrogen, then re-stored The reactor was heated to 70 ° C and pressurized with ethylene (100-120 psig, ca. 0.7-0.8 MPa). A sample of the mixture (C5Me5) Ti (02CPh) 3 / MeOH (0.33 ml, 1.92 x 10"6 mol Ti) was injected into the reactor and the temperature was allowed to rise to 85 ° C. The temperature was maintained between 80 and 85 ° C by the rest of the test, during this time ethylene flowed to recover the monomer lost by the polymerization. At a time of 30 min after the injection of the titanium complex, the reaction was quenched with methanol and the ventilated reactor. The polymer in hexane was recovered as a sticky mass that was broken and dried in vacuum overnight at 40 ° C, yielding 45.6 g of polymer with properties like rubber, for a catalyst activity of 48 kg (PE) / mmol ( Ti) «h» 100 psi C2 =. The polymer had MI = 0.09 and Fl = 2.2. The DSC of the copolymer showed melting points at 35.2, 65.9 and 115.9 ° C, with the last peak being about 3% as high as the dominant peak (65.9 ° C) and a total crystallinity of 17.3%; the peak recrystallization temperature was found at 52.9 ° C. SEC revealed Mw = 2.25 x 105 and MW / MN = 2.88. By rmn, the copolymer contained 25.0% by weight of 1-hexene.

Example 2 A second reduction of (CsMe5) Ti (02CPh) 3 / benzoic acid was obtained by vacuum reduction of the mother liquors of which the precursor used in Example 1 was filtered, cooled and filtered as in Example 1, which yielded a bright yellow powder. The second collection, however, still contained benzoic acid (1.4 eg for Ti). A toluene solution of (C5Me5) Ti (02CPh) 3 containing 1.4 eq. of benzoic acid (0.025 g in 5 ml, 7.0 mmol Ti / 1) was prepared under nitrogen. A mixture composed of 1 ml of the above solution and 0.32 ml of a solution of methanol in toluene (0.123 mol / 1, 0.039 mmol MeOH, MeOH / Ti = 5.6) was prepared and stirred for 90 min at room temperature. Drying by nitrogen stream while maintaining at 100 ° C for at least one h, the autoclave reactor was cooled, then charged with 650 ml of hexane, 40 ml of 1-hexene, 0.69 ml MAO (1.8 mol / l in toluene, 1.24 mmol Al), and 1.4 ml of a solution of DTBP in toluene (0.182 mol / 1, 0.25 mmol, Al / DTBP = 5.0). The reactor was heated to 40 ° C and vented to release most of the nitrogen, then resealed. The reactor was heated to 70 ° C and pressurized with ethylene (100-120 psig, ca, 0.7-0.8 MPa). A sample of the mixture (C5Me5) Ti (02CPh) 3 / MeOH (0.33 ml, 1.75 x 10"6 mol Ti) was injected into the reactor and the temperature was allowed to rise to 85 ° C. The temperature was maintained between 80 and 85 ° C for the remainder of the test, during this time ethylene flowed to complete the monomer lost for polymerization.At a time of 30 min after injection of the titanium complex, the reaction was quenched with methanol and the ventilated reactor. The polymer in hexane was recovered as a sticky mass that was broken and dried in vacuum overnight at 40 ° C, yielding 46.3 g of a polymer with properties such as rubber for a catalyst activity of 53 kg (PE) / mmol ( Ti) * h »100 psi C2 = The polymer had MI = 0.10 and Fl = 2.7 The DSC of the copolymer showed melting points at 35.8, 70.1 and 115.9 ° C, with the last peak being less than 10% as high as the dominant peak (70.1 ° C) and a total crystallinity of 15.1%, the peak recrystallization temperature is it reached 41.6 ° C. The SEC revealed Mw = 2.12 x 105 and MW / MN = 2.75. By rmn, the copolymer contained 25.7% by weight 1-hexene.

Example 3 A toluene solution of (C5Me5) Ti (02CPh) 3 containing 1.4 eq. of benzoic acid (0.025 g in 5 ml, 7.0 mmol Ti / 1) was prepared under nitrogen. A mixture was prepared composed of 1 ml of the above solution and 0.32 ml of a solution of methanol in toluene (0.123 mol / l, 0.039 mmol MeOH, MeOH / Ti = 5.6) which was stirred for 90 min at room temperature. Drying by stream of nitrogen while maintaining at 100 ° C for at least one h, the autoclave reactor was cooled, then charged with 650 ml of hexane, 40 ml of 1-hexene, 0.72 ml MMAO (1.74 mol / 1 in heptane, 2.25 mmol Al), and 1.4 ml of a solution of DTBP in toluene (0.182 mol / l, 0.25 mmol, Al DTBP = 5.0). The reactor was heated to 40 ° C and vented to release most of the nitrogen, then resealed. The reactor was heated to 70 ° C and pressurized with ethylene (100-120 psig, ca, 0.7-0.8 MPa). A sample of the mixture (C5Me5) Ti (02CPh) 3 / MeOH (0.33 ml, 1.75 x 10"6 mol Ti) was injected into the reactor and the temperature was allowed to rise to 80 ° C where it was maintained for the remainder of the Test, during which time ethylene flowed to complete the monomer lost by polymerization.At 30 min after injection of the titanium complex, the reaction was quenched with methanol and the vented reactor.The polymer in hexane was recovered as a viscous solution and dried under vacuum overnight at 40 ° C, yielding 19.2 g of a polymer with properties such as rubber, for a catalyst activity of 22 kg (PE) / mmol (Ti) »h * 100 psi C2 =. The polymer had MI = 0.05 and Fl = 1.24 The DSC of the copolymer showed melting points at 34.6, 67.5 and 116.7 ° C, with the last peak being about 3% as high as the dominant peak (65.7 ° C) and a crystallinity total of 14.8%, the peak recrystallization temperature was found at 45.5 ° C. The SEC revealed Mw = 2.63 x 105 and MW / MN = 2.94. By rmn, the copolymer contained 25.4% by weight of 1-hexene.

Example 4 Preparation of (C5Me5) Ti (02CCMe3) 3 All manipulations were carried out under a nitrogen atmosphere. A Schlenk flask was charged with stirring bar, 25 ml of anhydrous toluene and 2.0 g (C5Me5) TiCl3 (6.9 mmol). In a second flask were placed 2.11 g of pivalic acid (20.7 mmol) and stirrer, and the solution of (C5Me5) TiCl3 was transferred to it through a cannula. To the resulting orange mixture were added 2.9 ml (20.7 mmol) of triethylamine, and the solution was left stirring at room temperature for three hours and then filtered. The solid was washed with toluene, leaving it colorless. The filtrate was reduced to an orange oil in vacuum which then crystallized, from which 2.86 g (85%) were obtained. The nmr peaks of the titanium complex are as follows (d, solvent CD2CI2): ("" "H rmn) 1. (15H, s), 1. 09 (27H, s); "c ^ H J rmn) 194.4, 130.3, 38.7, 26. 56, 112.2 A solution in toluene of (CsMe5) Ti (02CCMe3) 3 was prepared (0.025 g in 5 ml, 10.3 mmol Ti / 1) under nitrogen. A mixture composed of 1 ml of the above solution and 0.32 ml of a solution of methanol in toluene (0.123 mol / 1, 0.039 mmol MeOH, MeOH / Ti = 3.8) was prepared and stirred for 35 min at room temperature. The stainless steel reactor dried by nitrogen flow while maintaining at 100 ° C for at least one hour (n) was cooled, then charged with 650 ml of hexane, 40 rrl of 1-hexene, 0.69 ml MAO (1.8 mol / 1 in toluene, 1.24 mmol Al) and 1.4 ml of a solution of DTBP in toluene (0.182 mol / 1, 0.025 mmol, Al / DTBP = 5.0). The reactor had two movable derailleurs inserted and a propeller in the form of a propeller, which was run at 800 rpm. The reactor was heated to 40 ° C and distilled to release most of the nitrogen, then resealed. The reactor was heated to 75 ° C and pressurized with ethylene (100 psig, 0.7 MPa) A sample of the mixture (C5Me5) Ti (02CCMe3) 3 / MeOH (0.33 ml, 2.5 x 10"6 mol Tí) was injected into the reactor and allowed to raise the temperature to 80 ° C, where it remained for the rest of the test, during this time ethylene flowed to complete the moromer lost by the polymerization.In a time of 30 min after the injection of the titanium complex, the reaction was quenched with methanol and the ventilated reactor, the polymer was recovered in hexane as a sticky mass that was broken and dried in vacuum overnight at 40 ° C, yielding a polymer with properties such as rubber, 52.8 g, a catalyst activity of 42 kg (PE) / mmol (Ti) «h * 100 psi C2 = .The polymer had MI = 0.17 and Fl = 4.4.

Example 5 The polymerization described in Example 2 was repeated, except that instead of the DTBP, 50 molar equivalents of benzoic acid (0.63 ml of a 0.2 mol / l toluene solution) were mixed with the MAO before polymerization. After work, 1.9 g of the polymer was obtained. The DSC of the copolymer showed melting points at 34.6 and 65.9 ° C and a total crystallinity of 15.1%; The peak recrystallization temperature was found at 44.2 ° C. The SEC revealed Mw = 3.27 x 105 and MW / MN = 3.57. By rmn, the copolymer contained 24.1% by weight of 1-hexene.

Examples 6-11 These examples demonstrate the use of the catalyst of this invention to copolymerize ethylene, propylene and ENB. In all of these examples the toluene was used as obtained (Aldrich Chemical Co., anhydrous, packed under nitrogen).

Example 6 In a glove box under nitrogen, a small oven-dried glass vial was charged with a magnetic stirrer and 0.025 g (C5Me5) Ti (02CPH) 3 containing 0.83 eq. of benzoic acid. This vial was sealed and taken out of the glove box. Toluene (5 ml) was added to the vial to form a solution with a concentration of 7.7 mmol / l. In another oven-dried glass vial sealed under nitrogen, 0.05 ml of methanol (MeOH) was mixed with 10 ml of toluene resulting in a solution of 0.123 mol / l MeOH / toluene concentration. In a third small glass vial dried in oven, 2.06 g of DTBP and 20 ml of toluene were added under nitrogen to form a solution of DTBP / toluene with a concentration of 0.5 mol / l. A small glass vial dried in an agitator oven was sealed under nitrogen. For this vial, 0.5 ml of (C5Me5) Ti (02CPh) 3 / toluene solution (0.00385 mmol Ti) and 0.16 ml of MeOH / toluene solution were mixed at room temperature for 60 minutes (MeOH / Ti = 5.1). A 100 ml glass bottle dried in an agitator oven was sealed with a diaphragm and purged with nitrogen. The following components were added to this bottle under nitrogen: 50 ml of hexane; 1.43 ml MMAO (1.74 mol (Al) / l in heptane); 1.0 ml of DTBP / toluene solution; 0.66 ml of the mixture prepared above (C5Me5) Ti (02CPh) 3 / MeOH and 2 ml of ENB. In this bottle the final active catalyst was formed with ratios of DTBP / Ti = 130, MeOH / Ti = 5.1, MMAO / Ti = 650. The reactor of 1 1, Fluitron, stainless steel, was heated for one hour at 100 ° C with constant flow of nitrogen through it. It was then cooled to 40 ° C and charged with 500 ml of hexane. The activated catalyst mixture prepared above was transferred to the reactor by nitrogen overpressure. The reactor was sealed and the temperature was brought to 60 ° C. Ethylene gases (C2 =) and propylene (C3 =) were charged (C3 = / C2 = fill ratio = 1: 1) were charged to the reactor until the reactor pressure reached 90 psi (0.62 MPa). The gas ratio was then adjusted to C3 = / C2 = 0.33. The polymerization was carried out for one hour after the introduction of the monomer gases. Two loads of ENB (0.5 ml) were injected into the reactor under pressure at the polymerization times of 10 min and 30 min. Therefore, 3 ml of total ENB were charged to the reactor. The polymerization was terminated by injection of 2 ml of destructive ethanol solution (0.5 g BHT, 1.0 g Kemamine, 0.5 g Irganox in 125 ml of ethanol). The flows of the monomer gases were cut off and the reactor was ventilated and cooled to room temperature. The polymer was drained, mixed in methanol and dried in a vacuum oven at 40 ° C overnight. The collected polymer weighed 12.0 g, for catalyst activity of 3.1 kg (EPDM) / mmol Ti / hr. The polymer had Fl = 0.52 and a P.R.T of 10.81 ° C. This demonstrated that MMAO can be used as a co-catalyst with (C5Me5) Ti (02CPh) 3 in the polymerization of EPDM.

Example 7 An experiment similar to Example 6 was carried out, except that a 2.86 ml solution of MMAO (1.74 mol / 1) (MMAO / Ti = 1290) was used. After polymerization, only 1.1 g of EPDM polymer was collected which shows much lower catalytic activity. This showed that the MMAO / (C5Me5) Ti (0CPh) 3 ratio is important for the polymerization activity of EPDM.

Example 8 A similar example as Example 6 was carried out except that a 0.86 ml solution of MMAO (1.74 mol / 1) was used.

(MMAO / Ti = 390). After polymerization, only 18. 2 g of EPDM polymer was collected for better catalytic activity of 4.7 kg (EPDM) / mmol Ti / h. The nmr analysis of the EPDM sample showed that it contained 31.8% by weight of propylene and 3.4% by weight ENB, and a PRT of 1.1 ° C. This further demonstrated that the MMAO / (C5Me5) Ti (02CPh) 3 ratio is important for the polymerization activity of EPDM.

Example 9 In a glove box under nitrogen, a small oven-dried glass vial was charged with a magnetic stirrer and 0.025 g (C5Me5) Ti (02CPH) 3 containing 0.83 eq. of benzoic acid. This vial was sealed and removed from the glove box. Toluene (5 ml) was added to the vial to form a solution with a concentration of 7.7 mmol / 1. In another oven-dried glass vial sealed under nitrogen, 0.05 ml of methanol (MeOH) was mixed with 10 ml of toluene resulting in a solution of 0.123 mol / l of MeOH / toluene concentration. In a third oven-dried small glass vial were added 2.06 g of 2,6-di-t-butylphenol (DTBP) and 20 ml of toluene under nitrogen to form a DTBP / toluene solution with a concentration of 0.5 mol / l. A glass vial dried in a small oven under nitrogen was sealed with a stirrer. For this vial, a solution of 0.5 ml of (C5Me5) Ti (? 2CPh) 3 / toluene (0.00385 mmol Ti) and 0.16 ml of MeOH / toluene solution at room temperature for 60 minutes (MeOH / Ti = 5.1 ). A 100 ml bottle of oven-dried glass with an agitator was sealed with a diaphragm and purged with nitrogen. To this bottle were added the following components under nitrogen: 50 ml of hexane; 0.30 ml MAO (3.36 mol / 1 in toluene); 1.0 ml of DTBP / toluene solution; 0.66 ml of the mixture prepared above (C5Me5) Ti (02CPh) 3 / MeOH and 2 ml of ENB. In this bottle the final active catalyst was formed with ratios of DTBP / Ti = 130, MeOH / Ti = 5.1, MMAO / Ti = 260. The 1 1 reactor, made of stainless steel, Fluitron, was heated for one hour at 100 ° C with nitrogen flowing constantly through it. This was then cooled to 40 ° C and charged with 500 ml of hexane. The activated catalyst mixture prepared above was transferred to the reactor by nitrogen overpressure. The reactor was sealed and the temperature brought to 60 ° C. Ethylene gases (C2 =) and propylene (C3 =) (C2 = / C3 = fill ratio = 1: 1) were charged to the reactor until the reactor pressure reached 90 psi (0.62 MPa). The gas ratio was then adjusted to C2 = / C3 = = 0.33. The polymerization was carried out for one hour after the introduction of the monomer gases. ENB (0.5 ml) was injected into the reactor under pressure at the polymerization times of 10 min and 30 min. Therefore, a total of 3 ml of ENB was charged to the reactor. The polymerization was terminated by injection of 2 ml of destructive ethanol solution (0.5 g BHT, 1.0 g Kemamine, 0.5 g Irganox in 125 ml of ethanol). The gases C2 = and C3 = were decreased and the reactor was ventilated and cooled to room temperature. The polymer was drained, mixed in methanol and dried in a vacuum oven at 40 ° C overnight. The collected polymer weighed 59.7 g, for a catalyst activity of 15.5 kg (EPDM) / mmol Ti / hr. The polymer had Fl = 1.32 and a P.R.T of -26.2 ° C.

Example 10 In a glove box under nitrogen, a glass vial dried in a small oven was charged with a magnetic stirrer and 0.024 g (C5Me5) Ti (02CCMe3) 3. This vial was sealed and removed from the handling box with gloves. . They were added to the vial (5 ml) of toluene to form a solution with a concentration of 0.01 mmol / 1. In another glass vial dried in an oven sealed under nitrogen, 0.05 ml of methanol was mixed with 10 ml of toluene resulting in a concentration of 0.123 mol / l of MeOH / toluene solution. In a third glass vial dried in a small oven, 2.06 g of 2,6-di-t-butylphenol (DTBP) and 20 ml of toluene were added under nitrogen to form a DTBP / toluene solution with a concentration of 0.5 mol / l. A small oven-dried glass vial was sealed with an agitator under nitrogen. In this vial were mixed 0.5 ml of solution (C5Me5) Ti (0CCMe3) 3 / toluene (0.005 mmol Ti) and 0.16 ml of MeOH / toluene solution at room temperature for 60 minutes (MeOH / Ti = 4). A 100 ml bottle of oven-dried glass with an agitator was sealed with a diaphragm and purged with nitrogen. The following components were added to this bottle under nitrogen: 50 ml of hexane; 0.30 ml MAO (3.36 mol / 1 in toluene); 1.0 ml of DTBP / toluene solution; 0.66 ml of the mixture prepared above (C5Me5) Ti (02CCMe3) 3 / MeOH and 2 ml of ENB. In this bottle the final active catalyst was formed with ratios of DTBP / Ti = 100, MeOH / Ti = 4, MMAO / Ti = 200. The reactor of 1 1, stainless steel, Fluitron, was heated for one hour at 100 ° C with constant flow of nitrogen through it. It was then cooled to 40 ° C and charged with 500 ml of hexane. The activated catalyst mixture prepared above was transferred to the reactor by nitrogen overpressure. The reactor was sealed and the temperature was brought to 60 ° C. The ethylene gases (C2 =) and propylene (C3 =) (C2 = / C3 = fill ratio = 1: 1) were charged to the reactor until the reactor reached the pressure of 90 psi (0.62 MPa). The gas ratio was then adjusted to C2 = / C3 = = 0.33. The polymerization was carried out for one hour after the introduction of the monomer gases. ENB (0.5 ml) was injected into the reactor under pressure at the polymerization times of 10 min and 30 min.

Therefore, a total of 3 ml of ENB was charged to the reactor. The polymerization was terminated by injection of 2 ml of destructive ethanol solution (0.5 g BHT, 1.0 g Kemamine, 0.5 g Irganox in 125 ml of ethanol). The gases C2 = and C3 = were cut and the reactor was ventilated and cooled to room temperature. The polymer was drained, mixed in methanol and dried in a vacuum oven at 40 ° C overnight. The collected polymer weighed 34.1 g, for a catalyst activity of 6.82 kg (EPDM) / mmol Ti / hr. The polymer contained 51.2% by weight of propylene and 4.5% by weight of ENB. The polymer had Fl = 1.6 and not PRT.

Example 11 An experiment similar to Example 10 was performed, except that 0.57 ml MMAO (1.74 mol (Al) / l in heptane) was used instead of MAO. The final active catalyst was formed with ratios of DTBP / Ti = 100, MeOH / Ti = 4, MMAO / Ti = 200. The collected polymer weighed 26.2 g, for a catalyst activity of 5.24 kg (EPDM) / mmol Ti / hr . The polymer did not flow due to its high molecular weight.

Comparative Example 1 A similar experiment as Example 6 was carried out except that it was used (C5Me5) iCl3 in place of the precursor of (C5Me5) Ti (0CPh) 3. After the polymerization, only 0.8 g of the polymer was collected. This experiment shows that (C5Me5) TiCl3 is not active with MMAO cocatalysts for polymerization of EPDM at a high aluminum: titanium ratio.

Comparative Example 2 A similar experiment as Comparative Example 1 was carried out, except that the molar ratios of aluminum: titanium were only 200: 1. After polymerization, 44.5 g of the polymer was collected for a catalyst activity of 8.90 kg (EPDM) / mmol Ti / hr. The polymer had Fl = 0.44 and a PRT of -34.8 ° C.

Claims (11)

1. A catalyst comprising: (A) a transition metal compound having the formula: (C5R15) TiY3, wherein each substituent R1 is independently selected from the group consisting of hydrogen, C? -C8 alkyl, an aryl and a aryl or alkyl substituted with heteroatom, with the proviso that not more than three substituents R1 are hydrogen; and wherein two or more substituents R1 may be linked together to form a ring; and each Y is independently selected from the group consisting of an amide of C? -C2o, a carboxylate of C1-C20 and a carbamate of C1.-C20; (B) a compound having the formula: R2OH or R3COOH wherein each R2 or R3 is a C? -C8 alkyl; and (C) an aluminoxane.

2. The catalyst of claim 1 wherein each Y is independently selected from the group consisting of a C? -C2o carboxylate and C? -C o -3 carbamate.

The catalyst of claim 1 further comprising: (D) a bulky phenol compound having the formula: (CeR45) OH, wherein each R4 group is independently selected from the group consisting of hydrogen, halide, a C? C8, an aryl, an alkyl or aryl substituted with heteroatom, wherein two or more R4 groups may be linked together to form a ring, and wherein at least one R4 is • represented by a linear or branched C3-C12 alkyl located in either or both at positions 2 and 6 of the bulky phenol compound.

4. The catalyst of claim 1 wherein a support or spray-drying material is employed.

5. The catalyst of claim 3 wherein the molar ratio of component B to component A varies 10 from about 2: 1 to 200: 1, the molar ratio of component C for component A ranges from about 5: 1 to 1000: 1; the molar ratio of component D for component A varies from about 10: 1 to 10,000: 1 with the proviso that 15 the ratio of component B for component D does not exceed 1: 1.

6. The catalyst of claim 5 further comprising as component E a spray-drying or support material in an amount ranging from 20 approximately 7 to 200 g / mmol.

7. The catalyst of claim 3 wherein each substituent R1 is a methyl group, R2OH is methanol; And it is selected from the group consisting of acetate, benzoate, pivalate and mixtures thereof; R4 is tert-butyl or Isopropyl; and the aluminoxane is modified methylaluminoxane.

8. A process for the polymerization of at least one olefin comprising contacting said low olefin • polymerization conditions with a catalyst consisting of: (A) a transition metal compound having the formula (C5R15) TiY3, wherein each substituent R1 is independently selected from the group consisting of hydrogen, C? -C8 alkyl, an aryl and an alkyl or aryl substituted with heteroatom, with the proviso that no more • which substituents R1 are hydrogen; and wherein two or more substituents R1 may be linked together to form a ring; and each Y is independently selected from the group consisting of an amide of C1-C20 a carboxylate of C1-C20 / and a carbamate of C1-C20 (B) a compound having the formula R2OH or R3COOH, wherein each R2 or R3 is a C? -C8 alkyl; and (C) an aluminoxane.

9. The process of claim 8 wherein each Y is independently selected from the group consisting of a 20 C 1 -C 20 carboxylate and a C 2 -C 2u carbamate.

10. The process of claim 8 wherein each R1 substituent is a methyl group; R 2 OH is methanol; And it is selected from the group consisting of acetate, benzoate, pivalate and mixtures thereof; and the aluminoxane is 25 modified methylaluminoxane.

11. The process of claim 8, wherein the catalyst further comprises: (D) a bulky phenol compound having the formula: (CeR5) OH, wherein each R4 group is independently selected from the group consisting of hydrogen, halide, an Ci-Cg alkyl, an aryl, an alkyl or aryl substituted with heteroatom, wherein two or more R4 groups can be linked together to form a ring, and wherein at least one R4 is represented by a linear or branched alkyl of C3-C12 ^^ 10 located in either or both of positions 2 and 6 of the bulky phenol compound.