MXPA00005189A - Catalyst components for the polymerization of dienes, catalyst obtained therefrom, and process for the preparation of polydienes using the same - Google Patents

Abstract

The present invention relates to a catalyst component comprising a compound of a metal selected from the group consisting of Co, Ni and rare earth elements supported on a polymer having a porosity (mercury) higher than 0.02 cm3/g. The use of the above catalyst component makes it possible to prepare dienic polymers, in gas-phase with high yields.

Description

CATALYST COMPONENTS FOR THE POLYMERIZATION OF DIENOS, CATALYST OBTAINED FROM THEM AND PROCEDURE FOR THE PREPARATION OF POLYDYNEN USING THEMSELVES DESCRIPTIVE MEMORY The present invention relates to a catalyst component for the preparation of polydienes, which is particularly suitable for use in processes where solutions are not employed. Polyene polymers are well known in the art. In particular, butadiene-based elastomers, which have a high content of cis-1,4 units, are very often used for the production of tires and other elastomeric products. In general, these products are obtained by solution polymerization using Z / N catalysts based on titanium, cobalt, nickel or lanthanide elements. Despite allowing the preparation of products of interest, in particular those with a high content of cis-1, 4 units, the solution procedure is not economical, since it requires the elimination of large quantities of solvent to obtain the solid products. In addition, the productivity of the procedure can not reach very high levels because the increase in the concentration of The polymer makes the viscosity of the polymerization medium so high that agitation is impossible. Accordingly, more economical and lower environmental impact procedures, such as gas phase procedures, would be desirable for the preparation of diene polymers. In order to achieve a viable gas phase process, the catalyst system employed must have the ability to produce polymers in high yields and with an optimum (possibly spherical) morphology. EP-A-647657 discloses a gas phase process for the polymerization of conjugated dienes by the use of a catalyst component consisting of a lanthanide element compound supported on a specific inorganic solid with certain surface area and porosity characteristics . According to this patent application, the above catalyst component has an activity higher than that of the catalyst component in which the solid inorganic support is absent; however, a higher activity would also be necessary to carry out an economic realization of a gas phase process. WO 96/04322 describes a gas phase process for preparing polydienes, carried out under conditions such as having the diene monomer (s) in the liquid state and in the presence of an inert particulate material. In accordance with that application, the above procedure must allow obtaining improved yields, as well as a reduction in polymer fouling. The catalyst system used in said process includes a metallic component of Ni, Co or Ti on a porous inorganic support, although black smoke is employed as the inert particulate material in the reactor. In view of the foregoing, it would be desirable to have a gas phase process for the preparation of polydienes which is characterized by the ability of simple operation, high productivity and reduction of fouling. In this regard, the term "simple operating capacity" includes avoiding the use of materials in the reactor other than monomers, catalyst system and fluidizing gas, and avoiding the use of restrictive polymerization conditions. It has been discovered with surprise that by using a catalyst system that includes a specific component and a cocatalyst, it is possible to perform such a process. Therefore, the objective of the present invention is a catalyst component for the polymerization of dienes comprising a compound of a metal selected from Co, Ni and lanthanide elements, supported on a polymer with porosity caused by pores with a radius of up to 100,000. A, greater than 0.02 cm3 / g measured by the mercury method specified below. The nickel compounds can be selected from organic nickel compounds with monodentate or bidentate organic solvents containing up to 20 carbon atoms. These organic nickel compounds are generally soluble in inert solvents. The representative elements of the organic nickel compounds are nickel benzoate, nickel acetate, nickel naphthenate, nickel octanoate, nickel neodecanoate, nickel 2-ethylhexanoate, bis (p-allyl-nickel), bis (cycloocta-1, 5- diene), bis (p-allyl-nickel-trifluoroacetate), bis (a-fur-idioxyl) -nickel, nickel palmitate, nickel stearate, nickel acetylacetonate, nickel salicydehyde, bis (salicylaldehyde) -ethylene; nickel-nickel, bis (cyclopentadiene) -nickel, nickel of cyclopentadienyl nickel and tetracarbonyl of nickel. Preferred nickel compounds are selected from nickel salts of carboxylic acids or organic nickel complexes. The cobalt compound can be any organic compound, such as the cobalt salts of organic acids, cobalt complexes and the like. Preferably, the cobalt compound is selected from the group consisting of cobalt-β-ketone complexes, for example, cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; β-ketoacid ester complexes of cobalt, for example cobalt acetylacetonate ethyl ester complexes, cobalt salts of organic carboxylic acids having 6 or more carbon atoms, for example, cobalt octoate, cobalt naphthenate and benzoate cobalt; and cobalt halide complexes, for example, cobalt-pyridine chloride complexes; complexes of cobalt chloride-ethyl alcohol and cobalt complexes coordinated with butadiene, for example, (1,3-butadiene) [1- (2-methyl-3-butenyl) -p-allyl] -cobalt which can be prepared, example, by mixing a cobalt compound with an organic aluminum compound, a lithium compound organic or a compound of alkylmagnesium and 1,3-butadiene. Other typical cobalt compounds are cobalt sorbate, cobalt adipate, cobalt 2-ethylhexoate, cobalt stearate, and similar compounds wherein the organic portion of the molecule contains about 5 to 20, preferably 8 to 18, atoms. carbon and one or two carboxylic functions, as well as acetylacetonate. The lanthanide metal compounds can be selected from the group consisting of: an alcoholate of formula (RO) 3M (I) - a carboxylate of formula (RCO 2) 3M (II); a lanthanide complex compound with diketones and / or a halogenide addition compound of the lanthanides with an oxygen or nitrogen donor compound corresponding to the following formulas: (R-CO-CH-CO-R) 3M (III) and ML3 »and donor (IV). In the above formulas M is a trivalent element of the lanthanides with atomic numbers from 57 to 71; the R groups can be the same or different and represent hydrocarbon radicals containing from 1 to 20 carbon atoms; L is chlorine, bromine or iodine; and, and is from 1 to 6. Preferred compounds are those wherein M is lanthanum, cerium, praseodymium, gadolinium or neodymium or a mixture of elements of the lanthanides containing at least 10% by weight of at least the following elements lanthanum, cerium, praseodymium or neodymium. Compounds wherein M is lanthanum or neodymium or a mixture of lanthanides containing at least 30% by weight of lanthanum or neodymium are more preferred. The substituents R in formulas (I) to (IV), in particular linear or branched alkyl radicals containing from 1 to 15 carbon atoms and preferably 1 to 10 carbon atoms, such as, methyl, ethyl, n-propyl , n-butyl, n-pentyl, isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, neopentyl, neooctyl, neodecyl, neododecyl. Examples of alcoholates of formula (I) are neodymium n-propanolate (III), neodymium n-butanolate (III), neodymium n-decanolate (III), neodymium isopropanolate (III), neodymium 2-ethylhexanolate ( lll), praseodymium n-propanolate (lll), praseodymium n-butanolate (lll), praseodymium n-decanolate (lll), praseodymium isopropanolate (lll), praseodymium 2-ethylhexanolate (lll), n-propanolate lanthanum (III), lanthanum n-butanolate (III), lanthanum n-decanolate (III), Lanthanum sopropanolate (III), lanthanum 2-ethylhexanolate (III). Preferred compounds are neodymium (III) n-butanolate, neodymium n-decanolate (III), and neodymium 2-ethylhexanolate (III). Suitable carboxylates of formula (II) are lanthanum propionate (III), lanthanum diethylacetate (III), lanthanum 2-ethylhexanoate (III), lanthanum stearate (III), lanthanum benzoate (III), lanthanum cyclohexanecarboxylate ( III), lanthanum oleate (III), lanthanum versatate (III), lanthanum naphthenate (III), praseodymium propionate (III), praseodymium diethylacetate (III), 2- praseodymium ethylhexanoate (III), praseodymium stearate (III), praseodymium benzoate (III), praseodymium cyclohexancarboxylate (III), praseodymium oleate (III), praseodymium versatate (III), praseodymium naphthenate (III), propionate of neodymium (III), neodymium diethylacetate (III), neodymium-2-ethylhexanoate (III), neodymium stearate (III), neodymium benzoate (III), neodymium cyclohexancarboxilate (III), neodymium oleate (III), neodymium versatate (III), neodymium naphthenate (III). Preferred compounds are neodymium 2-ethylhexanoate (III), neodymium versatate (III), and neodymium naphthenate (III). The neodymium versatate is of particular preference. Suitable complex compounds of formula (III) are lanthanum acetylacetonate (III), praseodymium acetylacetonate (III), neodymium acetylacetonate (III), and preferably neodymium acetylacetonate (III). Examples of addition compounds of formula IV are, for example, lanthanum chloride (III) with tributylphosphate, lanthanum chloride (III) with tetrahydrofuran, lanthanum chloride (III) with isopropanol, lanthanum chloride (III) with pyridine, lanthanum chloride (III) with 2-ethylhexanol, lanthanum chloride (III) with ethanol, praseodymium chloride (III) with tributylphosphate, praseodymium chloride (III) with tetrahydrofuran, praseodymium chloride (III) with isopropanol, praseodymium chloride (III) with pyridine, praseodymium chloride (III) with 2-ethylexanol, praseodymium chloride (III) with ethanol, neodymium chloride (III) with tributylphosphate, neodymium chloride (III) with tetrahydrofuran, neodymium chloride (III). with isopropanol, chloride neodymium (III) with pyridine, neodymium chloride (III) with 2-ethylhexanol, neodymium chloride (III) with ethanol, lanthanum bromide (III) with tributylphosphate, lanthanum bromide (III) with tetrahydrofuran, lanthanum bromide (III). ) with isopropanol, lanthanum bromide (III) with pyridine, lanthanum bromide (III) with 2-ethylhexanol, lanthanum bromide (III) with ethanol, praseodymium bromide (III) with tributylphosphate, praseodymium bromide (III) with tetrahydrofuran , praseodymium bromide (III) with isopropanol, praseodymium bromide (III) with pyridine, praseodymium bromide (III) with 2-ethylhexanol, praseodymium bromide (III) with ethanol, neodymium bromide (III) with tributylphosphate, bromide neodymium (III) with tetrahydrofuran, neodymium bromide (III) with isopropanol, neodymium bromide (III) with pyrridine, neodymium bromide (III) with 2-ethylhexanol, neodymium bromide (III) with ethanol. The lanthanide compounds can be used singly or mixed together. Another class of compounds that can be used in the preparation of catalysts for the polymerization of dienes is that of the lanthanide-allyl complexes. These compounds belong to the general formula (V): wherein the groups R- \ equal or different from each other are hydrogen or C1-C10 hydrocarbon groups, in particular alkyls; n is 1 or 2; X is selected from halides, carboxylates and alcoholates, and M has the meaning given previously. The complexes where M is Nd are preferred and among them, those of the following formula VI are particularly preferred: where the groups Ri and n have the same meanings given previously, X is Cl or Br, m is an integer from 0 to 2, p is an integer from 0 to 4, A is a salt of a metal that belongs to one of the groups I to IV of the Periodic Table of the Elements and ED is an electron donor compound. The fact that the complexes of the above formula (V) may be complexed with other molecules is probably a consequence of their preparation methods which often include the use of metal-allyl compounds and Nd halides as the starting material and certain electron donor compounds as a reaction medium.

In the above formula (VI) the preferred electron donor compounds are ethers and amines, and the preferred metal salts are MgCl2 and MgBr2. When the electron donor is ether preferably it is selected from the group consisting of diethyl ether, dimethoxyethane, tetrahydrofuran (THF) and dioxane.

Examples of allyl complexes that can be used are Nd (AIl) 2CM.5THF and Nd (Alil) CI2-2THF, the preparation of which is described in Journal of Organometallics Chem. (1998) 552, p. 195-204; and the complexes of formula Nd (Alil) 2C1 -2MgCl2-4THF (described in Macromol Symp. (1998) 128, pp. 53-61) and Nd (Alil) 2C1 -MgC12 nTHF where n is from 1 to 4. Sayings complexes, in which MgCl2 is also found, can generally be obtained by reacting, in an ether solvent, a Nd trihalogenide with an Mg-allyl halide. Preferably, the trihalide of Nd is NdCl 3, the ether solvent is tetrahydrofuran and the Mg-allyl halide is Mg-allyl chloride. The porous polymer is preferably selected from the group consisting of polyolefin (co) polymers. Preferably it is formed of polyethylene, ethylene copolymers with portions of less than 20 mol% of an olefin selected from propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, cyclopentene, cyclohexene, styrene; polypropylene with isotacticity index greater than 80%; crystalline propylene copolymers with smaller amounts (5 mol% or less) of ethylene, and / or α-olefins such as 1-butene, 1 -hexene. Said porous polyolefin polymer can be prepared by the polymerization of the monomers made in the presence of catalyst including the reaction product between an organic compound-AI and a solid catalyst component comprising a Ti, Zr, or V halide supported on MgCl 2. , said solid component with suitable characteristics depending on porosity and surface area to produce the polymers with the claimed porosity scale, preferably, said catalyst components have a spherical shape, with a particle size of 5 to 200 microns and with a surface area (BET) of less than 200. m2 / g and porosity (mercury method) for pores with a radius of up to 10,000 A, greater than about 0.5 cm3 / g and preferably greater than 0.6 cm3 / g. Examples of catalyst systems including solid components of this type are described, for example, in EP-A-395083, EP-A-553805, EP-A-553806 and EPA-601525. Said porous polymer may also be in a prepolymerized form which is a polymer obtained by low conversion polymerization using the catalysts described above. In general, the prepolymer is produced in an amount ranging from 0.5 g per g of solid catalyst component to 200 g / g. However, the preferred amount is between 5 and 500 g per g of solid component and more preferably between 10 and 100 g per g of solid component. In any case it is essential that the porosity (measured by the mercury method) is greater than 0.02 cm3 / g and preferably in the range of 0.04 to 1.4 cm3 / g, more preferably 0.04 to 1.2 cm3 / g as measured by the method of mercury described below. Particularly when a porous prepolymer is used, its porosity is preferably 0.3 to 1.2 cm3 / g, whereas when a porous polymer is used, its porosity is preferably 0.04 to 0.3. The porous polymer used in the present invention is also characterized by a porosity that is expressed as hollow percentage, greater than 10%, preferably greater than 15%. In addition, the porous polymer is also preferably provided with a spherical shape which can be obtained, for example, by using the catalyst components mentioned above. The metal compound can be supported on said porous polymer using various methods. The term "supported metal compound" as used herein means the metal compound that can not be extracted to a degree greater than 50% with heptane at 80 ° C for 2 hours. One method includes contacting the support and the metal compound in the presence of a liquid medium that is subsequently removed. Then, the catalyst component thus obtained is reacted with the suitable cocatalyst to form the final active catalyst. According to a preferred embodiment, instead, the metal compound is first converted to a final active catalyst by suitable reaction with the cocatalyst and then the entire system is supported on the porous polymer; therefore, this support method specifically includes: a) suspending the porous polymer in a hydrocarbon medium, preferably propane; b) that the mixture thus obtained makes contact with a mixture of hydrocarbon containing the metal component, the cocatalyst and optionally, a diene monomer; c) stirring the resulting mixture, and finally, d) removing the liquid hydrocarbon medium. Step b) is generally carried out by working at a temperature between 0 and 100 ° C, preferably between 10 and 60 ° C, while step c) is carried out for periods ranging from 1 minute to 10 hours. The use of a low-boiling hydrocarbon medium is preferred, since it is then possible to remove it easily by flash evaporation. Preferably, before performing step a), the porous polymer comes into contact with an Al-alkyl compound. The use of diisobutylaluminium hydride (DIBAH) is preferred. According to another embodiment, the support process can conveniently be carried out in a gas phase circuit reactor in which a stream of inert gas preserves the porous polymer in motion. The metal compound, optionally dissolved in hydrocarbon solvent, is introduced successively, for example by means of a sprinkler, into the gas phase circuit reactor, and a smooth flow product is obtained at the end of a treatment. As already mentioned, the active catalysts which can be used in the polymerization of dienes are formed by the reaction of the metal components with the suitable cocatalyst compounds. Suitable cocatalysts include organic compounds-AI in particular, the preferred organic-AI compounds are those of the formula AIHpRqXt, wherein R is a hydrocarbon group, preferably an alkyl group having from 1 to carbon atoms, X is halogen, preferably chlorine, p is 0 to 2, r is 1 to 3 and q is 0 to 2. Specific examples are triethylaluminum (TEAL), triisobutylaluminum (TIBA), tris chloride -2,3-dimethylbutylaluminum-diethylaluminum (DEAC), diisobutylaluminum hydride, and partially hydrolyzed diethyl aluminum chloride (DEACO). The alumoxanes can also be used as cocatalysts, in particular when the allyl-lanthanide complexes are used as catalyst components. In particular, the alumoxane that can be used is considered to be a linear, branched or cyclic compound containing at least one group of the type: wherein the substituents R7, equal or different from each other, are selected from the group consisting of hydrogen, C1-C20 alkyl radicals, cycloalkyl C3-C2o, C6-C20 aryl, C7-C2o alkylaryl, C7-C2o arylalkyl, saturated or unsaturated, linear or branched, optionally containing Yes or Ge, or R7 is a group -O-AI (R7) 2. In particular, linear alumoxanes have the formula: where m is an integer that goes from 0 to 40 and R7 has the meaning that was already indicated; and the cyclic alumoxanes have the formula: (Al-0) m where m is an integer ranging from 2 to 40, and R7 has the meaning that was already specified. In the aforementioned cyclic and linear alumoxanes, R7 is preferably methyl, ethyl, isobutyl or 2,4,4-trimethyl-pentyl. Examples of suitable alumoxanes as activating cocatalysts in the catalyst systems according to the present invention are methylalumoxane (MAO), a modified methylalumoxane which is obtained by substituting 20-80% of the methyl groups with an alkyl group of C2 to C12 preferably isobutyl (MMAO), isobutylalumoxane (TI BAO), 2,4,4-trimethyl-pentylalumoxane (TIOAO) and 2-methyl-pentylalumoxane. The mixtures of different alumoxanes can also be used. Suitable activating cocatalysts in the catalyst systems of the invention are also the reaction products between water and an organometallic aluminum compound, preferably of the formula AIR73 or Al2-R76, where R7 has the meaning already explained. In particular, the organometallic aluminum compounds described in EP 0 575 875 (formula (II)) and those described in WO 96/02580 (formula (II)) are suitable. Non-limiting examples of the organometallic aluminum compounds of the formula AIR73 or Al2R76 are: tris (methyl) aluminum, tris (isobutyl) aluminum, tris (isooctyl) aluminum, hydride of bis (isobutyl) -) aluminum, methyl-bis (isobutyl-) aluminum, dimethyl (isobutyl-) aluminum, tris (sodium) aluminium, tris (benzyl) aluminum, tris (tolyl) aluminum, tris (2,4,4-trimethylpentyl) aluminum, hydride of bis (2, 4,4-trimethylpentyl-) aluminum, isobutyl-bis (2-phenyl-propyl) aluminum, diisobutyl- (2-phenyl-propyl) aluminum, isobutyl-bios (2,4, 4-trimethylene-pentyl) aluminum and diisobutyl- (2,4,4-trimethyl-pentyl) aluminum. Particularly preferred aluminum compounds are tr, (2,4,4-trimethylpentyl) aluminum (TIOA), and triisobutylaluminum (TIBA). Mixtures of different organometallic aluminum compounds and / or alumoxanes can also be used. Suitable activating cocatalysts according to the present invention may also be compounds of formula Y + Z ", wherein Y + is a BrTnsted acid, capable of denoting a proton and of reacting irreversibly with a substituent X of the metal compound , and Z "is a compatible non-coordinating anion, capable of stabilizing the active catalytic species that are derived from the reaction of two compounds, and which has sufficient lability to be able to be displaced by an olefin substrate. Preferably, the anion Z "consists of one or more boron atoms More preferably, the anion TZ is an anion of the formula BAr4 (" -, wherein the substituents Ar, equal or different from each other, are aryl radicals, such as phenyl, pentafluorophenyl or bis (trifluoromethyl) phenyl .. The tetrakis-pentafluorophenyl borate is of particular preference In addition, the compounds of the formula BAr3 can be conveniently used.

When the metal compound is selected from Ni compounds, the cocatalyst is preferably selected from tritylaluminum (TEAL), tri (isobutyl) aluminum (TIBAL), diethylaluminum chloride (DEAC), MAO and mixtures thereof. In addition, promoters, including hydrogen fluoride, boron trifluoride and their stearate derivatives, are also preferably used. When the metal compound is selected from Co compounds, the cocatalyst is preferably selected from ethylaluminum sesquichloride (EASC), ethylaluminum dichloride (EADC), partially hydrolyzed diethylaluminum chloride (DEACO), MAO and mixtures thereof. When the metal compound is selected from lanthanide compounds, the cocatalyst is preferably selected from triethylaluminum (TEAL), tris (isobutyl) aluminum (TIBAL), diisobutylaluminum hydride (DIBAH), MAO and mixtures thereof. When the catalyst component contains as a metal compound the complexes of the formulas (V) - (VI), the cocatalyst is preferably MAO. When the metal compound is selected from those belonging to the formulas (I) - (III) and in particular Nd carboxylates, the catalyst system is conveniently prepared by reacting the Nd compound with an alkylating agent, and with a halogenation agent. The alkylating agent is preferably selected from the trialkylaluminum compounds, such as TIBAL, while the Halogenation is preferably selected from halogenated alkylaluminums such as DEAC or EASC. The molar ratios of Al / Nd and Cl / Nd of the catalyst are in some way critical for the polymerization activity. Preferably, the molar ratio of Al / Nd is greater than 10 and more preferably is between 15 and 70. The molar ratio of Cl / Nd is preferably greater than 2 and in particular is between 2.5 and 5. It has been observed that When the butadiene is to be polymerized, the activity of the catalyst system is improved as a consequence of the aging of the catalyst. In particular, the aging times of more than 2 days, and in particular between 10 and 40 days, are suitable for obtaining highly improved yields on the fresh catalyst. Even the order in which the Nd carboxylate, the alkylating agent and the chlorinating agent are added has an influence on the final properties of the catalyst. Often, the catalyst is first prepared by adding the chlorinating agent to the hydrocarbon solution of the Nd carboxylate., and then by reaction of the suspension mixture thus obtained with the alkylating agent. In the development of this method, contact of the first mixture with small amounts of the diene monomer before adding the alkylating agent has been found as a particular advantage for the increase in activity. In the alternative and preferred embodiment, the alkylating agent is first added to the hydrocarbon solution of the Nd carboxylate. Mix thus obtained (first mixture) then it is aged for a period greater than 4 hours, thus obtaining a homogeneous mixture which is then added with the halogenation agent. This technique makes it possible to obtain a final catalyst system which is completely soluble in the hydrocarbon medium and which is particularly suitable for support in the porous polymer. The aging time of the first preferred mixture is about one day, in particular when the carboxylates with at least 10 carbon atoms are used. For the lower carboxylates, longer times of aging are preferred, in particular from about 2 to 10 days. In general, the use of longer aging times of the first mixture generates a solution of the final catalyst system with the ability to remain transparent for periods longer than 5 days. Also, in this case, the aging of the final catalyst solution is beneficial for the activity. In particular, the aging time of about 2 to 4 days is preferred. The hydrocarbon medium used for the preparation of the catalyst system is generally selected from the group consisting of saturated hydrocarbons, such as propane, butane, pentane, hexane, heptane or aromatic hydrocarbons, such as toluene and benzene. As already explained, this catalyst system in particular is suitable for the preparation of polydienes by polymerization procedures carried out in the gas phase. In particular, it is very surprising that, as illustrated in the following examples, with the use of polymeric porous support of the invention it is possible to obtain improved yields with respect to those that can be obtained with the same catalyst system supported on silica, as described in the prior art. The gas phase process can be performed in a fluidized bed reactor or under conditions in which the polymer is mechanically stirred, and by the operation of one or more reactors. The polymerization temperature generally comprises between -10 and 250 ° C, preferably between 10 and 160 ° C. The pressure in general is between 0.1 and 50 bar and preferably between 1 and 20 bar. The molecular weight of the resulting polymers can be regulated by the use of molecular weight regulating agents or by the use of polymerization conditions. As polyene units capable of supplying units of unsaturation, conjugated and non-conjugated polyenes can be used. Among the conjugated dienes, 1,3-butadiene, isoprene, pentadiene or dimethylbutadiene can be used. The straight non-conjugated dienes may be selected from 1, 4- (cis or trans) -hexadiene, 6-methyl-1,5-heptadiene, 3,7-dimethyl-1, 6-octadiene, alkenyl or alkylidene norborne, such as 5-ethylidene-2-norbomene, 5-isopropylidene-2-norbomene, monocyclic diolefins, such as cis, cis-1,5-cyclooctadiene, 5-methyl-1,5-cyclooctadiene, 4,5,8,9 -tetrahydroindeno.

As is well known in the art, the dienes can also be used in mixtures with other monomers, such as styrene, to produce copolymers having specific properties. The polymers obtained with the catalyst of the invention have a cis-1,4 double bond content of about 60 to 99%. The molecular weight can be adjusted through the composition of the catalyst and by varying the polymerization conditions. Typical molecular weights range from 103 to 106, as measured by GPC (gel permeation chromatography). The viscosity of Mooney ML (1 + 4 ', 100 ° C) is almost always in the range of 30 to 180 MU. By means of the gas phase polymerization it is also possible to produce polymers of very high molecular weight which would be very difficult to obtain by solution polymerization, by the high viscosity and the possibility of transfer reactions through the solvent used. The polymer obtained can be compounded and vulcanized in the usual manner. The following examples are provided to better illustrate the invention without limiting it.

EXAMPLES Characterization Effective density: ASTM-D 792 Porosity (through pores with a radius of up to 100,000A): the measurement is made using a "Serial 2000 Porosimer" by Cario Erba Porosity is determined by the absorption of mercury under pressure. For this determination, a calibrated dilatometer (diameter 3 mm) CD3 (Cario Erba) connected to a mercury deposit and a high vacuum pump (1 * 10"2 mba) is used.A heavy amount of sample is placed in the dilatometer Then the device is placed under a high vacuum (<0.1 mm Hg) and kept under these conditions for 10 minutes, then the dilatometer is connected to the mercury deposit and the mercury is allowed to flow slowly in it until reaching the level marked in The dilatometer at the height of 10 cm The valve that connects the dilatometer to the vacuum pump is closed and then the mercury pressure is gradually increased with nitrogen up to 140 kg / cm2 Under the effect of the pressure, the mercury enters the the pores and the level descends according to the porosity of the material.The porosity (cm3 / g), and the pore distribution is calculated directly from the integral pore distribution curve that is the function of the reduction of the volume of the po and pressure values are applied (all these data are provided and processed by a computer related to the porosimeter that has a "MILESTONE 200 / 2.04" program by C. Erba. The porosity expressed as a percentage of holes is calculated from the following formula: X = (100-V) / V? where V is the volume of the pores and Vi is the apparent volume of the sample. The value of V is directly provided by the instrument that calculates it based on the difference between the initial and final level of the mercury. The apparent volume of the sample is given by V? = [P? - (P2-P)] / D where P is the weight of the sample in grams, Pi is the weight of the dilatometer + mercury in grams, P2 is the weight of the dilatometer + mercury + shows in grams and D is the density of the mercury (at 25 ° C = 13.546 g / cm3).

EXAMPLE 1 Support of the neodymium catalyst system 9.84 grams of a polyethylene prepolymer having a porosity of 0.341 cm 3 / g under nitrogen at room temperature was introduced into a 250 ml two-necked ball flask, which was then connected under nitrogen to a rotary evaporator. A solution that contains 5 DIBAH mmoles in 10 ml of hexane was added dropwise in 10 minutes. The flask was allowed to spin for 1 hour at room temperature under nitrogen. Then, the flask was disconnected from the rotary evaporator and the solid was dried under reduced pressure for 30 minutes at room temperature by gently stirring the flask to obtain a completely free fluid powder. Meanwhile, in a 25 ml Schlenk vessel containing a magnetic stirrer, a solution of 0.523 mmoles of Neodymium versatate (1.65 ml of a 0.317 M hexane solution), 0.2 mmoles of isoprene, 15 mmoles of DIBAH ( 10 ml of a solution in toluene 1.5 M) and 0.3 mmoles of EASC (2.5 ml of a solution in hexane 0.121 M). The solution was stirred for 5 minutes and then introduced into a cannula under nitrogen in the flask and distributed homogeneously in the solid support. The solid was dried under reduced pressure for 30 minutes by gently stirring the flask. Then the flask was weighed, and the weight of the supported catalyst was calculated as 12.4 grams.

Polymerization of 1, 3-butadiene The flask containing the supported catalyst prepared as described in the previous paragraph, was connected to rotovaporizador and allowed to rotate, at 80-100 rpm, she plunged in a water bath with temperature 40 ° C. 1,3-butadiene, already vaporized instantaneously twice and passed in a column of molecular sieves, it was introduced into the rotovaporizer and discharged continuously at a pressure of 0.26 barg. After 10 minutes, the gas phase polymerization was discontinued by stopping the introduction of 1,3-butadiene and with jets of nitrogen into the flask. 22.8 g of the solid containing 10.4 g of polybutadiene (99gpol activity / mmolNd / hr / baria) were obtained.

COMPARATIVE EXAMPLE Support of the catalyst system based on neodymium The same procedure described in Example 1 was followed, except that silica was used instead of the polyethylene prepolymer as the support for the catalyst system based on neodymium. 9.24 g of silica (Grace 955/60) was used as the support, after being dried at 250 ° C for 24 hours. 21.04 grams of the solid were obtained after the support of the catalytic system.

Polymerization of 1,3-butadiene The polymerization was carried out according to the procedure described in Example 1 with the only difference that the polymerization time lasted 1 hour. At the end of the polymerization 40 g of the solid were recovered, corresponding to 18.96 grams of polybutadiene (activity 30 gpol / mmoINd / h / baria).

EXAMPLE 2 Preparation of the homogenous catalyst solution A solution of hexane containing 0.361 mmol of Nd versatate was added with a hexane solution of TIBAL containing 10 mmol of Al. The solution thus obtained was allowed to remain for 1 day after which a solution of hexane containing 1.08 was added. mmol of DEAC. The resulting clear mixture, which had a molar concentration of 0.02, was then used in the next step.

Support of the neodymium catalyst system 15.3 grams of a polypropylene polymer having a porosity of 0.538 cm 3 / g under nitrogen and at room temperature in a 250 ml two-necked ball flask, containing hexane and then plugged in was introduced. under nitrogen to a rotary evaporator. The homogeneous catalyst solution prepared as described above was added dropwise in 10 minutes. The flask was allowed to spin for 30 minutes at room temperature under nitrogen. Then, the flask was disconnected from the rotary evaporator and the solid was dried under reduced pressure for 30 minutes at room temperature, gently shaking the flask, until obtaining a completely free fluid powder containing 0.34% Nd.

Polymerization of 1,3-butadiene The flask, which contained 7.85 grams of the supported catalyst prepared as described in the previous paragraph, was connected to the rotary evaporator and allowed to spin at 80-100 rpm, it was immersed in a water bath at room temperature . The 1,3-butadiene, already evaporated instantaneously twice and passed on a column of molecular sieves, was introduced into the rotovaporizer until it reached a pressure of about 1.2 atmospheres. After 15 minutes, the gas phase polymerization was discontinued by stopping the feed of 1,3-butadiene and with jets of nitrogen into the flask. 5 g of polybutadiene corresponding to an activity of 88gpol / mmolNd / h / baria were obtained.

Claims (33)

NOVELTY OF THE INVENTION CLAIMS

1. - A solid catalyst component for the (co) polymerization of dienes, comprising a compound of a metal that is selected from Co, Ni and lanthanide elements, supported on a polymer having a porosity due to pores with a radius of up to 100,000 A, greater than 0.02 cm3 / g that are measured by the mercury method.

2. A solid catalyst component according to claim 1, further characterized in that the porous polymer is selected from the group consisting of polyethylene, or ethylene copolymers with proportions less than 20 mol% of an olefin selected from propylene, 1-butene , 1-hexene, 4-methyl-1-pentene, 1-ketene, cyclopentene, cyclohexene, polypropylene with isotactivity index greater than 80%; crystalline copolymers of propylene with up to 5 mol% of ethylene and / or α-olefins, such as 1-butene, 1 -hexene.

3. A solid catalyst component according to claim 2, further characterized in that the porous polymer is a prepolymer produced in an amount of 0.5 to 2000 g per g of a solid catalyst component.

4. - A solid catalyst component according to claim 3, further characterized in that the porous polymer has a porosity in the range of 0.04 to 1.4 cm3 / g measured by the mercury method.

5. A solid catalyst component according to claim 1, wherein the porous polymer is further characterized by having a porosity, expressed as a percentage of gaps greater than 15%.

6. A solid catalyst component according to any of the preceding claims, further characterized in that the metal compound is selected from nickel compound with monodentate or bidentate organic ligands containing up to 20 carbon atoms.

7. A solid catalyst component according to any of claims 1-5, further characterized in that the metal compound is selected from cobalt salts of organic acids or organic cobalt complexes.

8. A solid catalyst component according to any of claims 1-5, further characterized in that the metal compound is selected from lanthanide compounds belonging to the following classes: an alcohol) of formula (RO) 3M (I); a carboxylate of formula (RCO2) sM (II); a lanthanide complex compound with diketones and / or an addition compound of the halides of the lanthanide with an oxygen or nitrogen donor compound corresponding to the formulas (R-CO-CH-CO-R) 3M (III) and ML3 * and donor (IV), where M is a trivalent element of the lanthanides with atomic numbers from 57 to 71; R groups can be the same 0 different and represent hydrocarbon radicals containing from 1 to 10 carbon atoms; L is chlorine, bromine or iodine; and, and is from 1 to 6.

9. A solid catalyst component according to claim 8, further characterized in that the metal compound is selected from those of the formula (II), wherein M is neodymium and wherein the substituents R are linear or branched alkyl radicals containing 1 to 10 carbon atoms.

10. A solid catalyst component according to claim 9, further characterized in that the carboxylates are selected from the group consisting of neodymium 2-ethylhexanoate (III), neodymium versatate (III), and neodymium naphthenate (III).

11. A solid catalyst component according to any of claims 1-5, further characterized in that the metal compound is selected from the lanthanide compounds of formula where the Ri groups or different groups from each other are hydrogen or C1-C10 hydrocarbon groups, in particular alkyls; n is 1 or 2; X is selected from halides, carboxylates and alcoholates, and M has the meaning given above.

12. - A solid catalyst component according to claim 11, further characterized in that M is Nd.

13. A solid catalyst component according to claim 12, further characterized in that the compound Nd is selected from those of the following formula (VI): where the groups R (and n have the same meanings given above, X is Cl or Br, m is an integer from 0 to 2, p is an integer from 0 to 4, A is a salt of a metal belonging to one of Groups I to IV of the Periodic Table of the Elements and ED is an electron donor compound.

14. A solid catalyst component according to claim 13, further characterized in that the electron-donor compound is selected from ethers and amines, and the metal salt is MgCl2 or MgBr.

15. A solid catalyst component according to claim 14, further characterized in that the electron donor is ether selected from the group consisting of dimethoxyethane of diethyl ether, tetrahydrofuran (THF) and dioxane.

16. The catalyst for the (co) polymerization of dienes comprising the reaction product of a solid catalyst component of according to any of the preceding claims with a cocatalyst.

17. The catalyst according to claim 16, further characterized in that the cocatalyst is selected from the group consisting of: organic compounds-AI of formula AIHpRqXt, wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, X is halogen, preferably chlorine, p is 0 to 2, r is 1 to 3 and q is 0 to 2; alumoxanes containing at least one group of the type: wherein the substituents R7, equal or different from each other, are selected from the group consisting of hydrogen, C1-C20 alkyl radicals, C3-C2o cycloalkyl, C6-C2o aryl. C7-C2o alkylaryl and C7-C2o arylalkyl saturated or unsaturated, linear or branched, optionally containing Si or Ge atoms, or R7 is a group -O-AI (R7) 2; compounds of formula Y + Z ", wherein Y + is a BrTnsted acid, capable of denoting a proton and reacting irreversibly with a substituent X of the metal compound, and Z" is a non-coordinating anion compatible, capable of stabilize active catalytic species that are derived from the reaction of two compounds, and that have sufficient lability to be able to be displaced by an olefin substrate.

18. The catalyst for the (co) polymerization of dienes comprising the reaction product of a solid catalyst component according to claim 6 and a cocatalyst selected from the group consisting of triethylaluminum (TEAL), tri (isobutyl) alum child (TIBAL), diethylaluminum chloride (DEAC), MAO and mixtures thereof.

19. The catalyst for the (co) polymerization of dienes comprising the reaction product of a solid catalyst component according to claim 7 and a cocatalyst selected from the group consisting of ethylaluminum sesquichloride (EASC), ethylaluminum dichloride ( EADC), partially hydrolyzed diethylaluminum chloride (DEACO), MAO and mixtures thereof.

20. The catalyst for the (co) polymerization of diamonds comprising the product of the reaction between a solid catalyst component according to any of claims 8-10 and an alkylating agent and with a halogenating agent.

21. The catalyst according to claim 26, further characterized in that the alkylating agent is selected from the trialkylaluminum compounds, and the halogenating agent is selected from halogenated alkylaluminums.

22. The catalyst for the (co) polymerization of dienes comprising the product of the reaction of a) a porous polymer with porosity caused by pores with a radius of up to 100,000 A, greater than 0.02 cm3 / g measured by the method of mercury, and b) the product of the reaction between (i) a metallic compound of lanthanides which belongs to one of the formulas (l) - (III) according to claim 12; (ii) an alkylation agent; and (iii) a halogenating agent, said components (i) - (iii) are reacted in a hydrocarbon medium.

23. The catalyst according to claim 22, further characterized in that the alkylating agent is selected from the trialkylaluminum compounds, and the halogenating agent is selected from the chlorinated alkylaluminums.

24. The catalyst according to claim 23, further characterized in that the lanthanide metal of the formulas (l) - (III) is Nd; the molar ratio of Al / Nd is between 30 and 70 and the molar ratio of Cl / Nd is between 2.5 and 6.

The catalyst according to claim 28, further characterized in that the reaction product b) is aged during a period greater than 2 days.

26. The catalyst according to claim 23, further characterized in that the component b) is obtained by the reaction of the component (iii) with a mixture, obtained by the contact between the components (¡) and (ii), which is has aged for a period exceeding 4 hours.

27. The catalyst according to claim 26, further characterized in that the mixture obtained by the contact of components (i) and (ii) is aged for a period exceeding 1 day.

28. - The process for the preparation of a catalyst component according to claims 1-15, characterized in that it comprises the contact of a compound of a metal selected from Co, Ni and lanthanide elements with a polymer having a porosity due to the pores with a radius of up to 100,000 A, greater than 0.02 cm3 / g measured by the mercury method.

29. The method according to claim 28, further characterized in that the contact is made in a liquid hydrocarbon medium.

30. The method according to claim 28, further characterized in that the contact is made in a gas phase.

31. The process for the (co) polymerization of dienes, further characterized in that it is carried out in the presence of a catalyst system in accordance with one or more of claims 16-27.

32. The method according to claim 31, further characterized in that the process is carried out in a gas phase.

33. The process according to claim 26, further characterized in that the diene is selected from the group consisting of 1,3-butadiene, isoprene, pentadiene or dimethylbutadiene, 1, 4- (cis or trans) -hexadiene, 6- methyl-1,5-heptadiene, 3,7-dimethyl-1,6-octadiene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, cis, cis-1, 5-cyclooctadiene, 5-methyl -1,5-cyclooctadiene, 4,5,8,9-tetrahydroindene.