MXPA00008831A - Polymerization of olefins - Google Patents

Abstract

Mixtures of different polyolefins may be made by direct, preferably simultaneous, polymerization of one or more polymerizable olefins using two or more transition metal containing active polymerization catalyst systems, at least one of which contains cobalt or iron complexed with selected ligands. The polyolefin products may have polymers that vary in molecular weight, molecular weight distribution, crystallinity, or other factors, and are useful as molding resins and for films.

Description

POLYMERIZATION OF OLEFINS FIELD OF THE INVENTION Polymers with varied and useful properties can be produced in processes using at least two polymerization catalysts, at least one of which is a selected iron or cobalt catalyst, for the synthesis of polyolefins.

TECHNICAL BACKGROUND Polyolefins are prepared more frequently by polymerization processes, in which a catalyst system containing transition metal is used. Depending on the process conditions used and the catalyst system chosen, polymers, even those made from the same monomer (s) may have variable properties. A part of the properties which can change are molecular weight and molecular weight distribution, crystallinity, melting temperature, branching, and vitreous transition temperature. Except for molecular weight and molecular weight distribution, branching can affect all the other properties mentioned.

Ref. 0122341 It is known that certain polymerization catalysts containing transition metal containing iron or cobalt are especially useful in polymerizing ethylene and propylene, see for example US Patent Applications 08/991372, filed on December 16. of 1997, and 09/006031, filed January 12, 1998 ("equivalents" of the World Patent Applications 98/27124 and 98/30612). It is also known that mixtures of different polymers, which vary for example in molecular weight, molecular weight distribution, crystallinity, and / or branching, can have advantageous properties in comparison to "unique" polymers. For example, it is known that polymers with broad or bimodal molecular weight distributions can often be processed by fusion (to be formed) more easily than polymers with narrower molecular weight distribution. Also, thermoplastics such as crystalline polymers can often be hardened by mixing them with elastomeric polymers.

Therefore, methods of producing polymers which inherently produce blends of polymers are useful especially if a separate (and expensive) separate polymer blending step can be avoided. However in such polymerizations one should be aware that two different catalysts can interfere with each other, or interact in such a way as to give a single polymer.

Several reports of oligomerization and "simultaneous" polymerization of ethylene to form (in some cases) branched polyethylenes have been published in the literature, see for example World Patent Application 90/15085, US Patents 5,753,785, 5,856,610, 5,686,542, 5,137,994 , and 5,071,927, C. Denger, et al., Makromol. Chem. Rapid Commun., Vol. 12, p. 697-701 (1991), and E. A. Benham, et al., Polymer Engineering and Science, vol. 28, p. 1469-1472 (1988). None of these references specifically describes any of the processes mentioned above or any of the branched homopolyethylenes claimed herein.

BRIEF DESCRIPTION OF THE INVENTION This invention relates to a process for the polymerization of olefins, which comprises, contacting under polymerization conditions: (a) a first active polymerization catalyst for olefins, which is a Fe or Co complex of a ligand of the formula: where : R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; Y R6 and R7 are aryl or substituted aryl; (b) a second active polymerization catalyst for the olefins, which contains one or more transition metals; (c) at least one first olefin capable of being polymerized by the first active polymerization catalyst; and (d) at least one second olefin capable of being polymerized by the second active polymerization catalyst.

This invention also relates to a process for the polymerization of defines, which comprises, contacting under polymerization conditions: (a) a first active polymerization catalyst for olefins, which is a Fe or Co complex of a ligand of the formula: where : R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; and Rs and R7 are aryl or substituted aryl; (b) a second active polymerization catalyst for the olefins, which contains one or more transition metals; (c) at least one first olefin capable of being polymerized by the first active polymerization catalyst, - and (d) at least one second olefin capable of being polymerized by the second active polymerization catalyst; and provided that: one or both of the first olefin and the second olefin is ethylene; one of the first polymerization catalyst and second polymerization catalyst produces an oligomer of the formula R60CH = CH2 from ethylene, wherein R60 is n-alkyl; Y A branched polyolefin is a product of the polymerization process.

This invention also relates to a polymerization catalyst component, which comprises: (a) a first active polymerization catalyst for olefins, which is a Fe or Co complex of a ligand of the formula: (i: where: R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; Y R6 and R7 are aryl or substituted aryl; (b) a second active polymerization catalyst for olefins, which contains one or more transition metals, - (c) a catalyst support; Y (d) optionally one or more polymerization catalyst activators for one or both of (a) and (b).

Also described herein is a polyolefin containing at least 2 ethyl branches, at least 2 hexyl branches or longer and at least one butyl branch per 1000 methylene groups, and provided that the polyolefin has less than 5 methyl branches per 1000 methylene groups.

This invention also includes a polyolefin, containing about 20 to about 150 branches of the formula - (CH 2 CH 2) n H, wherein n is an integer from 1 to 100, provided that the polyolefin has less than about 20 methyl branches per 1000 methylene groups.

DETAILS OF THE INVENTION In the polymerization processes and catalyst compositions described herein, certain groups may be present.

In term hydrocarbyl means a monovalent radical containing only carbon and hydrogen. The term "substituted hydrocarbyl" herein means a hydrocarbyl group, which contains one or more (types of) substituent atoms that do not interfere with the operation of the polymerization catalyst system. Suitable substituent atoms in certain polymerizations may include a part or all of halo, ester, keto (oxo), amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, amide, nitrile, and ether. Preferred substituent atoms are halo, ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, and amide. Which substituent atoms are useful in which polymerizations can be determined in certain cases by reference to U.S. Patent Applications 08/991372, filed December 16, 1997, and 09/006031, filed January 12, 1998 (and their corresponding World Patent Applications), both of which are hereby included by reference. The term "aryl" means a monovalent group whose free valence is for a carbon atom of an aromatic ring. The aryl part can contain one or more aromatic rings and can be replaced by inert groups. The term phenyl means the radical C6H5-, and a portion of phenyl or substituted phenyl is a radical in which one or more hydrogen atoms is replaced by a substituent group (which may include hydrocarbyl). Preferred substituent atoms for the substituted phenyl include those listed above for the substituted hydrocarbyl, in addition to the hydrocarbyl. If not otherwise indicated, the hydrocarbyl, substituted hydrocarbyl and all other groups containing carbon atoms, such as alkyl, preferably contain 1 to 20 carbon atoms.

The term "polymerization catalyst activator" means a compound that reacts with a transition metal compound to form an active polymerization catalyst. A preferred polymerization catalyst activator is an alkylaluminum compound, which is a compound which has one or more alkyl groups attached to an aluminum atom.

The term "polymerization catalyst component" means a composition that by itself, or after reaction with one or more other compounds (optionally in the presence of the olefins that are polymerized), catalyzes the polymerization of the olefins.

Non-coordinating ions are mentioned and useful here.

Such anions are well known to the skilled person, see for example W. Beck. , et al., Chem. Rev., vol. 88, p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are hereby included by reference. The relative coordination capabilities of such non-coordinating anions are described in these references, Beck on page 1411, and Strauss on page 932, Table III. Useful non-coordinating anions include SbF6", BAF, PF6", or BF4", where BAF is tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

A neutral Lewis acid or a Lewis or Bronsted cationic acid whose counter ion is a weak coordinating anion is also present as part of the catalyst system. The term "neutral Lewis acid" means a compound which is a Lewis acid capable of separating X from (II) to form a weak coordination anion.

In (II), M is Co or Fe, each X is independently an anion and each X is such that the total negative charges in X equals the oxidation state of M. The neutral Lewis acid is not originally charged (ie, it is non-ionic). Suitable neutral Lewis acids include SbF5, Ar3B (where Ar is aryl), and BF3. The term "cationic Lewis acid" means a cation with a positive charge, such as Ag +, H +, and Na *.

In those examples in which (II) does not contain an alkyl or hydride group already attached to the metal (i.e., X is not alkyl or hydride), the neutral Lewis acid or a Lewis or Bronsted cationic acid also alkylates or adds a hydride to the metal, i.e., causes an alkyl or hydride group to become attached to the metal atom, or a separate compound is added to add the alkyl or hydride group.

A preferred neutral Lewis acid, which can be alkylated to the metal, is a selected alkyl aluminum compound, such as R93A1, R92A1C1, R9A1CÍ2, and "R9AlO" (alkylaluminoxanes), wherein R9 is alkyl containing 1 to 25 carbon atoms , preferably 1 to 4 carbon atoms. Suitable alkylaluminium compounds include methylaluminoxane (which is an oligomer with the general formula [MeAlO] n), (C2H5) 2A1C1, C2H5AICI2, and [(CH3) 2CHCH2] 3A1. Metal hydrides, such as NaBH4, can be used to bind hydride groups to metal M.

For (I) and (II), preferred formulas and compounds are found in U.S. Patent Applications 08/991372, filed December 16, 1997, and 09/006031, filed January 12, 1998, and Preferred groupings and compounds are also preferred in these applications. However, the compound numbers and group numbers (ie, Rx) in these requests may vary from those 'mentioned here, but are easily convertible. These requests also describe the syntheses of (I) and (II).

There are many different ways of preparing the active polymerization catalysts from (I) or (II), many of which are described in US Patent Applications 08/991372, filed on December 16, 1997, and 09/006031, filed January 12, 1998, and those described in this way are applicable here. The "pure" compounds which themselves can be active polymerization catalysts can be used, or the active polymerization catalyst can be prepared in itself by a variety of methods.

For example, olefins can be polymerized by contacting, at a temperature of about -100 ° C to about + 200 ° C, a first compound W, which is a neutral Lewis acid capable of separating X "to form X" , provided that the anion formed is a weak coordination anion; or a Lewis or Bronsted cationic acid whose counterion is a weak coordination anion.

What early active polymerization catalysts will catalyze what olefins, and under what conditions, will also be found in U.S. Patent Applications 08/991372, filed December 16, 1997, and 09/006031, filed January 12, 1998 The monomers useful herein for the first active polymerization catalyst include ethylene and propylene. A preferred monomer for this catalyst is ethylene.

In another preferred process described herein, the first and second olefins are identical, and the preferred olefins in such a process are the same as described immediately above. The first and / or second olefins may also be a single olefin or a mixture of defines to make a copolymer. It is further preferred that they be identical, particularly in a process in which the polymerization by the first and second polymerization catalysts makes a polymer simultaneously.

In certain processes here, the first active polymerization catalyst can polymerize a monomer that can not be polymerized by the second active polymerization catalyst 7 and / or vice versa. In this case, two chemically different polymers can be produced. In another argument, two monomers would be present, with a polymerization catalyst that produces a copolymer, and the other polymerization catalyst that produces a homopolymer, or two copolymers can be produced, which vary in molar ratio or repeating units of the various monomers. Other analogous combinations will be apparent to the skilled person.

In another variation of the process described herein, one of the polymerization catalysts makes an oligomer of an olefin, preferably ethylene, whose oligomer has the formula R60CH = CH, wherein R60 is n-alkyl, preferably with a constant number of carbon atoms. The other polymerization catalyst in the process copolymerizes this olefin, either by itself or preferably with at least some other olefin, preferably ethylene, to form a branched polyolefin. The preparation of the oligomer (which is sometimes called α-olefin) by a first type of active polymerization catalyst can be found in U.S. Patent Application 09/005965, filed January 12, 1998 ("equivalent"). of the World Patent Application 99/02472), and BL Small, et. al., J. Am. Chem. Soc., vol. 120, p. 7143-7144 (19988), all of which are hereby included by reference. These references describe the use of a limited class of compounds, such as (II) to prepare compounds of the formula R60CH = CH2 from ethylene, and thus qualify as a catalyst that produces this olefin. In a preferred version of this process, one of these first types of polymerization catalyst is used to form the α-olefin, and the second active polymerization catalyst is a catalyst which is capable of copolymerizing ethylene and olefins of the formula R60CHCH2, such as a Ziegler-Natta or metallocene type catalyst. Other types of such catalysts include transition metal complexes of amidimidates and certain iron or cobalt complexes of (I). The amount of branching due to the incorporation of the olefin R60CH = CH2 into the polymer can be controlled by the ratio of the polymerization catalyst that forms the α-olefin to the olefin polymerization catalyst which forms the higher polymer. The larger the proportion of polymerization catalyst that forms the higher α-olefin is the amount of branching. The homopolyethylenes that are made can vary from polymers with little branching to polymers which contain many branches, that is, from highly crystalline homopolyethylene to amorphous. In a preferred form, especially when a crystalline polyethylene is made, the process is carried out in the gas phase. It is believed that in many cases in the gas phase polymerization when both catalysts are present in the same particle in which the polymerization is taking place (for example, originally a supported catalyst), especially the α-olefin (polymerized in the resulting polymer) is used efficiently. When the amorphous or crystalline homopolyethylenes are made only slightly, the process can be carried out in liquid slurry or solution.

In the variation of the process described in the preceding paragraph immediately, a new Ineopolis homopoly is produced. The term "homopolyethylene" in this example means a polymer produced in a polymerization in which ethylene is the only polymerizable olefin added to the one-step polymerization process, reactor, or by simultaneous reactions. However, it is understood that the polymer produced is not made by the direct polymerization of ethylene alone, but by the copolymerization of ethylene and α-olefins which are produced in itself. The polymer produced usually contains only branches of the formula (excluding end groups) - (CH2CH2) nH, where n is 1 or more, preferably 1 to 100, more preferably 1 to 30, of these branches per 1000 atoms of methylene. Normally, there will be branches with an "n" range in the polymer. The amount of these branches (as measured by the total methyl groups) in the polymer preferably ranges from about 2 to about 200, especially preferably about 5 to about 175, more preferably about 10 to about 150, and especially preferably about 20 to about 150 branches per 1000 methylene groups in the polymer (for the method of measurement and calculation, see World Patent Application 96/23010). Another preferable range for these branches is about 50 to about 200 methyl groups per 1000 carbon atoms of methylene. It is also preferable (either alone or in combination with other preferable features above) that in these branched polymers there be at least 2 branches each of ethyl and n-hexyl or longer and at least one n-butyl branching per 1000 groups of methylene, more preferably at least 4 branches each of ethyl and n-hexyl or longer and at least 2 branches of n-butyl per 1000 methylene groups, and especially preferably at least 10 branches each of ethyl and n'-hexyl or long ma and at least 5 branches of n-butyl per 1000 methylene groups. It is also preferred that there be more ethyl branches than butyl branches in this homopolyethylene. In another preferred polymer (alone or in combination with any of the above preferred characteristics) there are less than 20 methyl branches, preferably less than 2 methyl branches, and especially preferably less than 2 methyl branches (all after the correction for the final groups) per 1000 methylene groups.

In the polymerizations for making the "homopolyethylene" only a single high molecular weight polymer is produced, that is to say a polymer which has an average degree of polymerization of at least 50, more preferably at least 200, and especially so preferably at least 400. The synthesis of the branched homopolyethylene is believed to be successful in part because the catalyst which produces the α-olefin often in this manner at a rate comparable to the polymerization rate, both for the low cost reason, It's relatively fast.

Likewise, the conditions for such polymerizations, particularly for the catalysts of the first type of active polymerization, will also be found in all of these patent applications. Briefly, the temperature at which the polymerization is carried out is about -100 ° C to about +200 ° C, preferably about -20 ° C to about + 80 ° C. The polymerization pressure which is used with a gaseous olefin is not critical, being a suitable range from atmospheric pressure to approximately 275 MPa, or more. With a liquid monomer, the monomer can be used pure or diluted with another liquid (solvent) for the monomer. The ratio of: (I), when present, is preferably about 1 or more, preferably about 10 or more when only W (no other Lewis acid catalyst) is present. These polymerizations can be batch, semi-batch or continuous processes, and can be carried out in a liquid medium or the gas phase (assuming that the monomers have the required volatility). These details will also be found in U.S. Patent Applications 08/991372, filed December 16, 1997, and 09/006031, filed January 12, 1998, and 09/005965, filed January 12, 1998. .

In these polymerization processes, the preferred groups for R6 is and for R7 it is where: R8 and R13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R9, R10, -R11, R14, R15 and R1S are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R12 and R17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that any two of R8, R9, R10, R11, R12, R13, R14, R15, R1S and R17 that are adjacent to each other, taken together can form a ring.

Two chemically active active polymerization catalysts are used in the polymerization described herein. The first active polymerization catalyst is described in detail above. The second active polymerization catalyst can also comply with the limitations of the first active polymerization catalyst, but must be chemically distinct. For example, it may have a different transition metal present, and / or use a ligand which differs in structure between the first and second active polymerization catalysts. In a preferred process, the type of ligand and the metal are the same, but the ligands differ in their substituent atoms.

Within the definition of two active polymerization catalysts, systems are included in which a single polymerization catalyst is added in conjunction with another ligand, preferably the same type of ligand, which can displace the original ligand coordinated to the metal of the original active polymerization catalyst, to produce in your two different polymerization catalysts.

However, other types of catalysts can also be used for the second active polymerization catalyst. It is also possible to use, for example, Ziegler-Natta and / or metallosose type catalysts, so-called. These types of catalysts are well known in the field of polyolefins, see for example Angew. Chem., Int. Ed. Engl., Vol. 34, p. 1143-1170 (1995), European Patent Application 416,815 and U.S. Patent Application 5,198,401 for information about metallocene-type catalysts, and J. Boor Jr., for Ziegler-Natta type catalysts and polymerizations, Academic Press, New York, 1979 for information about Ziegler-Natta type catalysts, all of which are hereby included by reference. Suitable recent transition metal catalysts will be found in World Patent Applications 96/23010 and 97/02298, both of which are hereby included by reference. Many of the polymerization conditions useful for these types of catalyst and the first active polymerization catalysts coincide, so that the conditions for the polymerizations with the first and second catalysts. Active polymerization are easily accessible. Sometimes the "cocatalyst" or "activator" is needed for the polymerizations with metallocene or Ziegler-Natta type catalyst, both W is sometimes necessary for the polymerizations using the first active polymerization catalysts. In many examples the same compound, such as an alkylaluminum compound, can be used for these purposes for both types of polymerization-catalysts.

Suitable catalysts for the second polymerization catalyst also include metallocene-type catalysts, as described in U.S. Patent Application 5,324,800 and European Patent Application 129,368; Particularly advantageous are the bis-indenyl metallocenes bleached, for example as described in U.S. Patent Application 5,145,819 and European Patent Application 485,823. Another class of suitable catalysts comprises the well-known forced geometry catalysts, as described in European Patent Applications 416,815, 420,436, 671,404, and 643,066 and World Patent Application 91/04257. The class of transition metal complexes described in WO 96/13529 can also be used. Also useful are transition metal complexes of bis (carboximidamide), as described in United States Patent Application 08/096668, filed September 1, 1998.

All the catalysts here can be "heterogeneous" (to form a polymerization catalyst component, for example) by coating or otherwise attaching them to solid supports, such as silica or alumina. Where a species of active catalyst is formed by reaction with a compound, such as an alkylaluminum compound, a support in which it is first coated or otherwise bound, the alkylaluminum compound is contacted with the metal compounds of transition (or its precursors) to form a catalyst system in which the active polymerization catalysts are "bound" to the solid support. These supported catalysts can be used in polymerizations in organic liquids. They can also be used in so-called gas phase polymerizations, in which the olefin (s) being polymerized are added to the polymerization as gases and no liquid support phase is presented. The transition metal compounds can also be coated on a support, such as a polyolefin backing (polyethylene, polypropylene, etc.), optionally together with other necessary catalyst components, such as one or more alkylaluminium compounds.

The molar ratio of the first active polymerization catalyst to the second active polymerization catalyst used will depend on the polymer ratio of each desired catalyst, and the relative rate of polymerization of each catalyst under the process conditions. For example, if one needs to prepare a "hardened" thermoplastic polyethylene containing 80% crystalline polyethylene and 20% rubber-like polyethylene, and the polymerization rates of the two catalysts were equal, then a molar ratio of 4 would be used: 1 of the catalyst that gave crystalline polyethylene to the catalyst that gave rubbery polyethylene. More than two active polymerization catalysts can also be used if the desired product contains more than two different types of polymer.

The polymers made by the first active polymerization catalyst and the second active polymerization catalyst can be made in sequence, that is, one polymerization with one (either first or second) of the catalysts, followed by a polymerization with the other catalyst, using two series polymerization vessels. However, it is preferred to carry out the polymerization using the first and second polymerization catalysts active in the same vessel (s), that is, simultaneously. This is possible because in many examples the first and second active polymerization catalysts are compatible with each other, and produce their different polymers in the presence of the other catalyst.

The polymers produced by this process can vary in molecular weight. and / or molecular weight distribution and / or melting temperature and / or level of crystallinity, and / or vitreous transition temperature or other factors. For the copolymers, the polymers can differ in proportions of comonomers if the different polymerization catalysts polymerize the monomers present at different relative speeds. The polymers produced are useful as molding and extrusion resins and in films as for packaging.

These may have advantages, such as improved melt processing, hardness and improved low temperature properties.

In the Examples, all pressures are gauge pressures.

In the Examples, the transition metal catalysts were either purchased, or if a distributor was not quoted, they were made. The synthesis of nickel-containing catalysts will be found in World Patent Application 96/23010, while the synthesis of catalysts containing cobalt and iron will be found in US Patent Applications 08./991372, filed on December 16. of 1997, and 09/006031, filed on January 12, 1998.

In the Examples, PMAO-IP is a form of methylaluminoxane, which remains in solution in toluene, and is commercially available. W440 is a Ziegler-Natta type catalyst of unknown structure from Akzo Chemicals, Inc., 1 Livingston Ave. Dobbs Ferry, NY 10522, U.S.A.

Examples 1-9 and Comparative Examples A-E General Procedure for Ethylene Polymerization The catalyst was weighed in a reaction vessel and dissolved in approximately 20 mL of distilled toluene. The reaction was sealed and transferred from the dry compartment to the smoke hood. The reaction was purged with nitrogen, then with ethylene. Then PMAO-IP (metialuminoxane solution) was quickly added to the vessel and the reaction was placed under 35 Kpa ethylene. The reaction proceeded at room temperature in a water bath to help dissipate the heat of any exotherm. The ethylene was then removed and the reaction was rapidly cooled with approximately 15 mL of methanol / HCl solution (90/10% volume). If the polymer was introduced, the reaction was filtered and the polymer rinsed with methanol, then with acetone and dried overnight in the smoke hood. The resulting polymer was collected and weighed.

The catalysts used are listed below for each polymerization.

Example 1 Catalyst 1: 4 mg (0.006 mmol) Catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog # 93-4002, 2 mg (0.006 mmol).

C! Cl cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2. OM in toluene duration: 4 hours polymer: 5322 g of yield Example 2 Catalyst 1: 4 mg (0.006 mmol) Catalyst 2: 4 mg (0.006 mmol) cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2.0M in toluene duration: 4 hours polymer: 2282 g of yield Example 3 Catalyst 1: 3.5 mg (0.006 mmol) Catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog # 93-4002, 2 mg (0.006 mmol) cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2.0M in toluene duration: 4 hours polymer: 3,651 g of yield Example 4 Catalyst 1: 3.5 mg (0.006 mmol) Catalyst 2: 4 mg (0.006 mmol) cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2.0M duration: 4 hours polymer: 2890 g of yield Example 5 Catalyst 1: 3.5 mg (0.006 mmol) Catalyst 2: 4 mg (0.006 mmol) cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2.0M in. toluene duration: 4 hours polymer: 3,926 g of yield Example 6 Catalyst 1: 4 mg (0.006 mmol) Catalyst 2: W440, from Akzo Nobel, Ti at 2.3% by weight, 12 mg (0.006 mmole of Ti, based on% by weight) cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2.'0M in toluene duration: 4 hours polymer: 2,643 g of yield Example 7 Catalyst 1: 3.5 mg (0.006 mmol) Catalyst 2: W440, from Akzo Nobel, Ti at 2.3% by weight, 12 mg (0.006 mmole of Ti, 'based on% by weight) cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2.0M in toluene duration: 4 hours polymer: 2.943 g of yield Example 8 Catalyst 1: 4 mg (0.006 mmol) Catalyst 2: 4 mg (0.006 mmol) Catalyst 3: Zirconocene dichloride, from Strem Chemicals, catalog # 93-4002, 2 mg (0.006 mmol) Cl Cl cocatalyst: PMAO-IP; 3.0 mmol of Al; 1.5t mL of 2.0M in toluene duration: 4 hours polymer: 6,178 g of yield Example 9 Catalyst 1: 3.5 mg (0.006 mmol) Catalyst 2: 4 mg (0.006 mmol) Catalyst 3: Zirconocene dichloride, from Strem Chemicals, catalog # 93-4002, 2 mg (0.006 mmol) cocatalyst: PMAO-IP; 3.0 mmol of Al; 1.5 mL of 2.0 M in toluene duration: 4 hours polymer: 4,408 g of yield Example A Comparative .catalyst: zirconocene dichloride, from Strem Chemicals, catalog # 93-4002, 2 mg (0.006 mmol) Cl cocatalyst: PMAO-IP; 1.0 mmol of Al; 0.5 mL of 2.0M in toluene duration: 4 hours polymer: 2.936 g of yield Example B Comparative Catalyst: 4 mg (0.006 mmol) cocatalyst: PMAO-IP; 1.0 mmol of Al; 0.5 mL of 2.0M in toluene duration: 4 hours polymer: 1.053 g of yield Example C Comparative Catalyst: 4 mg (0.006 mmol) cocatalyst: PMAO-IP; 1.0 mmol of Al; 0.5 mL of 2.0M duration: 4 hours polymer: 2.614 g of yield Example D Comparative Catalyst: 3.5 mg (0.006 mmol) cocatalyst: PMAO-IP; 1.0 mmol of Al; 0.5 mL of 2. OM in toluene duration: 4 hours polymer: 2,231 g of yield Example E Comparative catalyst: W440, from Akzo Nobel, Ti at 2.3% by weight, 12 mg (0.006 mmol of Ti, based on% by weight) cocatalyst: PMAO-IP; 1.0 mmol of Al; 0.5 mL of 2.0M in toluene duration: 4 hours polymer: 0.326 g of yield Examples 10-12 General Procedure for Polymerization of Propylene The catalyst was weighed in a reaction vessel and dissolved in approximately 20 mL of distilled toluene. The reaction was sealed and transferred from the dry compartment to the smoke hood. The reaction was purged with nitrogen, then with propylene. Then MAO was rapidly added to the vessel and the reaction was placed under 35 Kpa propylene. The reaction proceeded at 0 ° C in a water bath. Then the propylene was removed and the reaction was rapidly cooled with approximately 15 mL of methanol / HCl solution (90/10% volume). If the polymer was introduced, the reaction was filtered and the polymer rinsed with methanol, then with acetone and dried overnight in the smoke hood. The resulting polymer was collected and weighed.

Example 10 1: 3 mg catalyst (0.006 mmol) Catalyst 2: Zirconocene dichloride, from Strem Chemicals, catalog # 93-4002, 2 mg (0.006 mmol) Cl Cl cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2. OM in toluene duration: 5 hours polymer: 0.471 g of yield Example 11 1: 3 mg catalyst (0.006 mmol) Catalyst 2: 4 mg (0.006 mmol) cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2.0M in toluene duration: 5 hours polymer: 1,191 g of performance Example 12 1: 3 mg catalyst (0 .006 mmol) Catalyst 2: W440, from Akzo Nobel, Ti at 2.3% by weight, mg (0.006 mmole of Ti, based on% by weight) cocatalyst: PMAO-IP; 2.0 mmol of Al; 1.0 mL of 2.-0M toluene duration: 5 hours polymer: 0.238 g of yield Examples 13-77 and Comparative Examples F-N In these Examples, compounds A-V and 2 were used as transition metal compounds.

H For the preparation of: compound A see B. L. Small, et al., J. Am. Chem. Soc., Vol. 120, p. 7143-7144 (1998); Compound B see Ewen, et al., J. Am. Chem. Soc., vol. 110, p. 6255-6256 (1998); Compound C see European Patent Application 416,815; compound D see World Patent Application 98/27124; compound E see World Patent Application 96/23010; Compounds G, H, I and R were purchased from Boulder Scientific company; compounds K, P and 2 were purchased from Strem Chemicals Inc .; Compound Q was obtained from Aldrich Chemical Co .; compounds S, T, Ü and V were made by the methods described in United States Patent Application 08/096668, filed September 1, 1998; Compound F was made by reacting ZrCl4 and the lithium amide salt (see J. Chem. Soc., Dalton Trans. 1994, 657) in ether overnight, and removing the ether and extracting pentane gave F in a yield of 69%; Compound J was prepared by modifying the procedure of Journal of Organometallic Chemistry 1993, 459, 177-123; compounds L and M were prepared following the preparation in Macromolecules, 1995, 28, 5399-5404, and Jorunal of Organometallic Chemistry 1994, 472, 113-118; compound N was made by the process described in U.S. Patent Application 5,096,857; and Compound O was prepared following a literature procedure (Ferdinand R. W. Wild, et al., Journal of Organometallic Chemistry 1985, 288, 63-67).

Examples 13-17 and Comparative Examples F-G A Parr® 600 mL reactor was heated under vacuum and then allowed to cool under nitrogen. In a dry compartment, to a Hoke® cylinder was added 5 mL of toluene and a certain amount of PMAO-IP (13.5% by weight toluene solution) as shown in Table 1. To a 20 mL bottle is added the ethylene copolymerization catalyst and 2 mL of toluene. Then the solution was transferred using a pipette to a RB flask. 300 mL, followed by the addition of 150 mL of 2, 2, 4-trimethyl pentane. If catalyst A was used, its toluene suspension was transferred using a syringe to the flask. The flask was capped with a rubber septum. Both the Hoke® cylinder and the flask were removed from the dry compartment. Under nitrogen protection, the transition metal compound solution was introduced by means of a cannula into the reactor. The reactor was pressurized with nitrogen and then the nitrogen was released. The reactor was heated to 70 ° C, then 2X to 690 kPa of ethylene was pressurized, vented each time and finally pressurized to 970 kPa with stirring. The MAO solution was added to the Hoke® cylinder at a slightly higher pressure. Then the ethylene pressure of the reactor was adjusted to the desired pressure (Table 1). The reaction mixture was allowed to stir for a certain period of time (Table 1). The heating source was removed. The ethylene was vented to about 210 kPa. The reactor was again filled with 1.4 MPa nitrogen and then vented to 210 kPa. This was repeated once. Then the reaction mixture was cooled to RT (room temperature). Then the reaction mixture was poured slightly into 400 mL of methanol, followed by the addition of 6 mL of concentrated HCl. With stirring at RT for 25 minutes, the polymer was filtered, washed with methanol six times and dried in vacuo.

Examples 18-76 (except Examples 22 and 23) and Comparative Examples H-N General procedure for making silica-supported catalysts: In a dry compartment, one of the transition metal compounds (but not A), and compound A (0.1% by weight in biphenyl) and MAO supported on silica (18% by weight in Al, Albermarle) were mixed with 15 mL of toluene in a 20 mL flask. The flask was shaken for 45 minutes at RT.

The solid was filtered, washed with 3x5 mL of toluene and dried under vacuum for 1 hour. It was then stored in a refrigerator in the dry compartment and used the same day.

General procedure for the polymerization of ethylene in gas phase by supported catalysts using a Harper Block Reactor: In a dry compartment, the supported catalysts were weighed in GC bottles (5.0 mg or 2.0 mg each, except Example 20 where 15.0 was used. mg), were placed in a Harper Block Reactor. The reactor was removed from the dry compartment and charged with 1.21 Mpa of ethylene. Then it was placed in an oil bath at 90 ° C for 1 hour under 1.12 Mpa of ethylene. The temperature of the reactor reached 85 ° C after 23 minutes and 87 ° C after 35 minutes. The temperature remained at 87 ° C for the rest of the reaction. (Time, temperature and pressure for the Examples in Tables 7-9, as noted). The ethylene was vented. The polymers were weighed and then subjected to XH NMR analysis (TCE-d2, 120 ° C) without purification. The details of these polymerizations are given in Table 2-9.

In Table 10, the distribution of the branching [in branches per 1,000 methylene groups (CH 2)] of the product polymers of the selected examples is given. They were determined by 13 C NMR (TCB, 120 ° C). Methods for measuring branching distribution are found in World Patent Application 96/23010.

In all the Tables, where provided, the branching levels in the polymers, groups of Me / 1000CH2, methyl groups per 1000 methylene groups in the polymer, are measured by the method described in the World Patent Application 96/23010 .

In the Tables, PE is polyethylene, TON is moles of polymerized ethylene / mol of polymerization catalysts (total of transition metal compounds present) / hour, Mn is the average molecular weight number, PDI is Mw / Mn, where Mw it is the average molecular weight by weight, and P is ethylene pressure. The PMAO-IP used was 13.5% by weight in toluene. The amount of residual α-olefin in the polymer was estimated by 1 H NMR, by measurement of the α-olefin vinyl proton signals.

Table 1 -p »00 * Bimodal distribution due to α-olefins Table 2 • P » Table 3 or Table 4 in Table 5 * Table 6 Ol ro Table 7 * i * Two o'clock at 70 ° C and a pres e n e e n e at 2.4 pa Table 8 * One hour at 90 ° C, at an electric pressure of 2.4 Mpa. Table 9 * oí * Two hours at 60 ° C, pressure and 2.4 Mpa Table 10 Example 22 In a dry compartment, 1.7 mg of Compound E and 1.0 mg of Compound A were mixed with 40 mL of toluene in a Schlenk flask. This was taken out of the dry compartment and purged with ethylene for 15 minutes at 0 ° C. The MAO toluene solution (0.64 mL, 13.5% by weight) was injected. The mixture was allowed to stir under ethylene of 0 kPa at 0 ° C for 12 minutes. Methanol (100 mL) was injected, followed by 1 mL of concentrated HCl. With stirring for 25 minutes at RT, the white solid was filtered, washed with 6x20 mL of methanol and dried in vacuo. White solid was obtained (2.9 g). XH NMR in TCE-d2 at 120 ° C: 44Me / l000CH2. The polymer contained a significant amount of α-olefins. Example 23 In a dry compartment, 30.5 mg of Compound A was mixed with 30.5 g of biphenyl in a 100 mL Pyrex® glass bottle. This was stirred in a 100 ° C bath for 25 minutes, during which time Compound A was dissolved in biphenyl to form an intense green solution. The solution was allowed to cool until it became solid. A homogeneous mixture of Compound A / biphenyl at 0.1% by weight was obtained.

Example 77 A 600 mL Parr® reactor was heated under vacuum and then allowed to cool under nitrogen. In a dry compartment, 150 mL of 2, 2, 4-trimethylpentane was added to a 300 mL RB flask. The flask was capped with a rubber septum. The flask was removed from the compartment. Under nitrogen protection, the 2, 2, 4-trimethylpentane solvent was introduced via a cannula into the reactor. The reactor was pressurized with nitrogen and then the nitrogen was released. This was repeated one more time. The reactor was heated to 70 ° C. Then in a dry compartment, 160 mg of supported catalyst (made following the general procedure of preparing silica supported catalysts, this contained 0.0011 mmoles of compound B, 0.000057 mmoles of compound A and 1.1 mmoles of MAO) was mixed with 4 mL of cyclohexane and transferred to a 5 mL gas tight syringe with a long needle. This was removed from the dry compartment and injected into the reactor under nitrogen protection (positive nitrogen pressure). The reactor was pressurized with 1.2 MPa of nitrogen, then released to 14 kPa. This was repeated one more time. With stirring, the reactor was pressurized with ethylene at 1.2 Mpa. The reaction mixture was allowed to stir at 70 ° C to 97 ° C for 60 minutes. The heating source was removed. The ethylene was vented to about 210 kPa. The reactor was again filled with 1.4 MPa nitrogen and freed up to 140 kPa. This was repeated twice. The solution was poured into 300 mL of methanol. The polymer was filtered, washed with 6x50 mL of methanol and dried in vacuo. White polymer was obtained (19.7 g). 1 H NMR in TCE-d2 at 120 ° C: 34Me / l000CH2. Mw =. 98,991; Mn = 35,416 (PDI = 2.8). Density: 0.902g / cm3. Melt index: 1.03 (190 ° C). 13C NMR (120 ° C, TCE-d2): Me total was 29.4 (Me = 0, Et = 10.8, Pr = 0.0, Bu = 6.0, Hex and greater = 11.7).

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (24)

DJ. CLAIMS

1. A process for the polymerization of olefins, characterized in that it comprises, contacting under polymerization conditions: (a) a first active polymerization catalyst for olefins, which is a Fe or Co complex of a ligand of the formula: ; D where: R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; Y R6 and R7 are aryl or substituted aryl; (b) a second active polymerization catalyst for the olefins, which contains one or more transition metals; (c) at least one first olefin capable of being polymerized by the first active polymerization catalyst; Y (d) at least one second olefin capable of being polymerized by the second active polymerization catalyst.

2. The process according to claim 1, characterized in that the second active polymerization catalyst is a Ziegler-Natta or metallocene type polymerization catalyst.

3. The process according to claim 1 or 2, characterized in that the first define and the second olefin are both ethylene.

4. The process according to claim 1 or 2, characterized in that the first olefin is ethylene.

5. The process according to claim 1 or 2, characterized in that the first olefin and the second olefin are each independently one or both of ethylene or propylene.

6. The process according to claim 1, characterized in that the polymerization with the first active polymerization catalyst and the polymerization with the second active polymerization catalyst are carried out in a simultaneous manner.

7. The process according to claim 1, characterized in that the first olefin and the second olefin are the same.

8. A process for the polymerization of olefins, characterized in that it comprises, contacting under polymerization conditions: (a) a first active polymerization catalyst for olefins, which is a Fe or Co complex of a ligand of the formula: (i; where: R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; Y R6 and R7 are aryl or substituted aryl; (b) a second active polymerization catalyst for the olefins, which contains one or more transition metals; (c) at least one first olefin capable of being polymerized by the first active polymerization catalyst; and (d) at least one second olefin capable of being polymerized by the second active polymerization catalyst; and condition that: one or both of the first olefin and second olefin is ethylene; one of the first polymerization catalyst and second polymerization catalyst produces an oligomer of the formula R60CH = CH2 from ethylene, wherein R60 is n-alkyl; Y A branched polyolefin is a product of the polymerization process.

9. The process according to claim 8, characterized in that the first define and the second olefin is ethylene, and other polymerizable olefins are not added.

10. The process according to claim 8 or 9, characterized in that the complex is a Fe complex and the first olefin is ethylene.

11. The process according to claim 8 or 9, characterized in that the first polymerization catalyst is a Fe complex and produces the oligomer.

12. The process according to claim 8, characterized in that the process is carried out in the gas phase.

13. A polymerization catalyst component, characterized in that it comprises: (a) a first active polymerization catalyst for olefins, which is a Fe or Co complex of a ligand of the formula: where : R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group; R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl; Y R6 and R7 are aryl or substituted aryl; (b) a second active polymerization catalyst for the olefins, which contains one or more transition metals; (c) a catalyst support; Y (d) optionally one or more polymerization catalyst activators for one or both of (a) and (b).

14. The polymerization catalyst component according to claim 13, characterized in that one of the first polymerization catalyst and the second polymerization catalyst produces an oligomer of the formula R CH = CH2 from ethylene, wherein R 60 is n-alkyl.

15. The polymerization catalyst component according to claim 13, characterized in that the second active polymerization catalyst is a Ziegler-Natta or metallocene-type polymerization catalyst.

16. The polymerization catalyst component according to claim 14, characterized in that the second active polymerization catalyst is a Ziegler-Natta or metallocene-type polymerization catalyst.

17. The polymerization catalyst component according to claim 13, characterized in that the support is alumina, silica or a polyolefin.

18. The polymerization catalyst component according to claim 13, characterized in that (d) is present and is an alkylaluminum compound.

19. The polymerization catalyst component according to claim 13, characterized in that the second polymerization catalyst is a transition metal complex of a bis (carboximidamidatonate).

20. The polymerization catalyst component according to claim 14, characterized in that the second active polymerization catalyst is a transition metal complex of a bis (carboximidamidatonate).

21. A polyolefin, characterized in that it contains at least 2 ethyl branches, at least 2 branches of hexyl or longer and at least one branching of butyl per 1000 methylene groups, and provided that the polyolefin has less than 5 methyl branches per 1000 methylene groups.

22. A polyolefin, characterized in that it contains about 20 to about 150 branches of the formula - (CH 2 CH 2) n H, wherein n is an integer from 1 to 100, provided that the polyolefin has less than about 20 methyl branches per 1000 groups of methylene and provided that a range of at least three branches of n different values are present.

23. The polyolefin according to claim 21, characterized in that it is a homopolyethylene.

24. The polyolefin according to claim 22, characterized in that it is a homopolyethylene.