SK5502002A3 - Catalyst compositions, methods of polymerization, and polymers therefrom - Google Patents

Abstract

The present invention provides catalyst compositions useful in polymerization processes, including a Group 15 containing metal compound, mixed catalyst compositions including the Group 15 containing metal compound and a second metal compound which is preferably a bulky ligand metallocene catalyst, supported and unsupported catalyst systems thereof, and a process for polymerizing olefin(s) utilizing them. The invention also discloses a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.

Description

CATALYTIC COMPOSITIONS, POLYMERIZATION METHODS AND POLYMERS MADE IN THESE METHODS

Technical field

The present invention relates to a catalyst composition comprising a metal compound comprising a Group 15 element of the Periodic Table of the Elements and a mixed catalyst composition comprising at least two metal compounds. In a preferred embodiment, at least one of the metal compounds constituting said catalyst composition is a metal compound comprising a Group 15 element of the Periodic Table of the Elements. In an even more preferred embodiment, the further metal compound is a sterically bulky ligand metallocene catalyst compound. Furthermore, the present invention relates to catalyst systems based on said compositions and their use in the polymerization of olefin (s). Furthermore, the present invention relates to a novel polyolefin, usually polyethylene, in particular a muitimodal polymer, in particular a bimodal polymer, and its use in various end products such as film, molded article and tube.

BACKGROUND OF THE INVENTION

Advances in polymerization and catalysis have made it possible today to produce new polymers having improved physical and chemical properties that are suitable for use in a wide range of products and applications with excellent properties. Along with the development of new catalysts, there has been a large expansion in the choice of a possible type of polymerization (i.e., solution, suspension, high pressure or gas phase polymerization) that is suitable for the production of a particular polymer. Advances in polymerization have also made more efficient, highly productive and economically advantageous processes available. These advances can be illustrated, in particular, by the development of technology using metallocene-based catalyst systems with sterically bulky ligands.

The results of recent research have led to the discovery of anionic, multidentate heteroatom ligands, which have been described in the following

31925 / T R R publications: (1) Kempe et al., "Aminopyridinato Ligands - New Directions and Limitations ,,, 80 ^th Canadian Society for Chemistry Meeting, Windsor, Ontario, Canada, 1 to 4 June 1997 (2) Kempe et al., Inorg. Chem., 1996, 35, 6742; (3) Bei, X., Swenson, DC, Jordan, RF, Organometallics, 1997, 16, 3282; (4) Horton et al., &Quot; Cationic Alkylzirconium Complexes Based on a Tridentate Diamide Ligand: NewAlkene Polymerization Catalysts ", Organometallics, 1996, 15, 2672-2674, concerning tridentate zirconium complexes; (5) Baumann et al., "Synthesis of Titanium and Zirconium Complexes that Contain the Tridentate Diamido Ligand [((t-Bu-d6) NO-C6H 4) 2 O] ² '{[NON]} ² ·) and the Living Polymerization of 1-Hexene by Activated [NON] ZrMe 2, Journal of the American Chemical Society, 119, 3830-3831; (6) Cloke et al., "Zirconium Complexes Incorporating the New Tridentate Diamide Ligand [(Me ₃ Si) N {CH ₂ CH ₂ N (SiMe ₃ } ₂ ] ² '(L); the Crystal Structure of [Zr (BH4 (2L) and [ZrCl {CH (SiMe 3) 2} L] ", J. Chem. Soc. Dalton Trans., 1995, 25-30; (7) Clark et al.," Titanium (IV) Complexes Incorporating the Aminodiamide Ligand [(SiMe3) N {CH 2 CH 2 N (SiMe 3) 2] ² '(L); the X-ray Crystal Structure of [TiMe 2 (L)] and [TiCI {CH (SiMe ₃ ) ₂ } (L)] " of Organometallic Chemistry, 1995, 50, 333-340; (8) Scollard et al., "Living Polymerization of Alpha-Olefins by Chelating Diamide Complexes of Titanium," J. Am. Chem. Soc., 1996, 118, 10 And (9) Guerin et al., Conformationally Rigid Diamide Complexes: Synthesis and Structure of Titanium (IV) Alkyl Derivatives, Organometallics, 1996, 15, 5085-5089.

In addition, U.S. Pat. No. 5,576,460 describes the preparation of arylamine ligands, and U.S. Pat. No. 5,889,128 discloses a process for the polymerization of olefins to form a so-called olefin polymer. living polymers (i.e., polymers with an active group at the end of the chain) and using initiators comprising a metal atom and a ligand comprising two 15th atoms and one 16th group atom or three 15th group atoms. European Patent Application Publication No. EP 893 454 also describes preferred amide compounds containing as a transition metal

31925 / T • «· r

f) titanium. Furthermore, U.S. Patent No. 5,318,935 discusses amide compounds of transition metals and catalyst systems based on these compounds, which are particularly suitable for the production of isotactic polypropylene. Polymerization catalysts containing bidentate and tridentate ligands are further described in U.S. Patent No. 5,506,184.

The use of traditional bulky ligand metallocene catalyst systems results in polymers which in some cases are difficult to process into foil, for example using an old extrusion apparatus. One possibility of improving the properties of these polymers is to mix these polymers with other polymers to form a blend that has the desired properties that the individual components would have used alone. Although the two-component polymer blends are better processable, their manufacture is expensive and leads to the inclusion of a relatively cumbersome mixing stage in the manufacturing / processing process.

The higher molecular weight imparts the desired mechanical properties to the polymer and results in stable sleeve formation in the film production. However, this property also prevents extrusion processing of the polymers by increasing the back pressure in the extruders during processing, promoting the formation of melt breakage when stretching the sleeve and potentially promoting the formation of too high a degree of orientation in the resulting film. Said anionic, multidentate, heteroatom-containing catalyst systems tend to form very high molecular weight polymers. This problem can be solved by simultaneously forming a secondary, minor component of lower molecular weight, which serves to reduce back pressure in the extruder and prevent melt fracture. Several industrial processes are based on this principle, using several reactors for the production of high density polyethylene (HDPE) with bimodal molecular weight distribution (MWD). Mitsui's HDPE product is considered the worldwide standard in this regard

31925 / T • c · e c e * o r r c r

C r r p

Chemicals sold under the designation HIZEX®, wherein HIZEX® is produced by a costly process using two or more reactors.

Another approach to solving the above problem is the simultaneous production of two different polymers in one reactor by using two different catalysts in this reactor. WO 99/03899 discloses the use of a typical sterically bulky ligand metallocene catalyst and a conventional Ziegler-Natta catalyst in a single reactor to produce a bimodal polyolefin. However, the use of two different types of catalysts leads to the formation of a polymer whose properties cannot be predicted by the properties of the polymers that would have arisen if the individual catalysts were used separately. This unpredictability of the properties of the resulting polymer is due, for example, to competitive reactions or to other influences between the catalysts or catalyst systems used.

Higher density and molecular weight polyethylenes are used in the production of films having high rigidity, toughness and high overall strength. Such polymers are also used in the manufacture of tubes where it is necessary for the tubes to have good rigidity, toughness, long life and, in particular, to be resistant to cracking caused by ambient loads.

Therefore, there is a need for improved catalyst compounds and catalyst mixtures in which processable polyethylene polymers could be produced, preferably in a single reactor, characterized by the desired combination of processability, mechanical and optical properties.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide catalyst compounds, catalyst systems and mixed catalyst systems, polymers produced using these compounds and systems, and products made from such polymers.

One aspect of the present invention is a metal catalyst compound comprising a Group 15 element, a mixed

· Catalyst composition comprising at least two metal compounds, wherein at least one of said metal compounds is a metal compound comprising an element of

The 15th group of the Periodic Table of the Elements and another metal compound is a sterically bulky ligand metallocene, and a conventional transition metal catalyst or mixture thereof. Further, the invention in this aspect relates to catalyst systems comprising said catalysts, their use in the polymerization of one or more olefins and the polymers thus produced.

A further aspect of the present invention is a Group 3 to 14 catalytic metal compound catalyst comprising a Group 15 element, wherein said Group 3 to 14 metal, preferably from 3 to 7 a group of the Periodic Table of the Elements, more preferably from

Group 4-6, and more preferably group 4 substituted by a bi- or tridentate ligand, a mixed catalyst composition comprising at least two metal compounds, wherein the at least one metal compound is a metal compound containing the element of 15 above. a group of the Periodic Table of Elements wherein the other metal compound is a sterically bulky ligand metallocene and a conventional transition metal catalyst or mixture thereof. Further, the invention in this aspect relates to catalyst systems comprising said catalysts, their use in polymerization, one or more olefins and the polymers thus produced. In this embodiment, it is preferred that the further metal compound is a sterically bulky ligand metallocene.

Another aspect of the invention is a catalytic compound in which there is an atom

Group 3-14 metal bonded to at least one leaving group and further to at least two member atoms of Group 15, at least one of which atoms is also bonded to the element atom through another group Group 15 or 16, a mixed catalyst composition comprising at least two metal compounds, wherein at least one metal compound is the above-described metal compound comprising a Group 15 element.

31925 / T c r

^r . rr, rrr of the array of elements, wherein the second metal compound differs from the first metal compound, the metal compound being a sterically bulky ligand metallocene, and a conventional transition metal catalyst or mixture thereof. Further, the invention in this aspect relates to catalyst systems comprising said catalysts, their use in the polymerization of one or more olefins and the polymers thus produced.

Another aspect of the present invention is a method of depositing the above-described catalyst compositions on a suitable carrier, the catalyst systems themselves supported on a suitable carrier, and their use in the polymerization of one or more olefins.

A further aspect of the present invention is the use of an aluminum-containing Lewis acid activating agent together with the catalyst compositions and systems of the invention.

Another aspect of the present invention is a process for injecting the catalyst compositions and systems of the present invention contained in a liquid carrier into a polymerization reactor.

Another aspect of the present invention is a process for the polymerization of one or more olefins in the gas phase or in suspension, using any of the catalyst systems described herein or any of the supported catalyst systems described herein.

Another aspect of the present invention is a process for the polymerization of one or more olefins using the catalyst compositions described above, in particular in a single polymerization reactor. More preferably, the process uses a single continuous gas phase reactor to form a multimodal polymer.

Another aspect of the invention are polymers made using the above mixed catalyst composition, in particular novel high density polyethylenes with a bimodal molecular weight distribution (referred to below as HDPE with a bimodal MWD).

31925 / T e e r p c c e PC r e p r r. r · Γ p P c p r

P P P p f r '‘.r ¾'

The present invention relates to the use of a catalytic metal compound comprising a Group 15 element of the Periodic Table of the Elements in the polymerization of one or more olefins. In addition, it has been found that the use of these catalytic metal compounds containing a Group 15 element in combination with another catalyst, preferably a sterically bulky ligand metallocene, results in the formation of HPDE with a bimodal MWD. Unexpectedly, it was then found that the mixed catalyst composition of the present invention can be used in a single reactor system.

A metal compound containing an element of group 15 of the Periodic Table of the Elements

A compound comprising a Group 15 element of the Periodic Table of the Invention typically comprises a metal atom of Group 3-14, preferably Group 3 to 7, more preferably Group 4-6. and most preferably from group 4 of the Periodic Table of the Elements which is bound to at least one leaving group and further to at least two atoms of the elements of Group 15 of the Periodic Table of Elements, at least one of these atoms being bound to the atom of 15th or 16th group of the periodic system of elements.

In one embodiment of the present invention, at least one of the 15th group atoms of the Periodic Table of the Elements is attached to the 15th or 16th Group element of the Periodic Table through another group, which further group may be a hydrocarbon group containing from 1 to 20 carbon atoms, heteroatom, silicon, germanium; tin, lead or phosphorus, where the atom of the 15th or 16th element of the Periodic Table of Elements also need not be attached to any group or may be bound to a hydrogen atom, to the group containing the 14th element of the Periodic Table of Elements, halogen or to a group containing a heteroatom, wherein each of the two atoms of the elements of the 15th group of the Periodic Table of the Elements may also be bound to the cyclic group and may be

31925 / T is optionally bonded to a hydrogen, halogen, heteroatom or hydrocarbon group or a heteroatom-containing group.

According to another embodiment of the present invention, the structure of a metal compound comprising a Group 15 element of the Periodic Table of the Elements can be represented by the general formula I or II:

R ⁴

R ¹ Y.

R ⁶

R ³ ·

MnXn + m

R ³

R ⁷ (I) or wherein

(Ii)

M is a transition metal atom of Groups 3-12 of the Periodic Table of the Elements or a metal atom of Group 13 or 14 of the Periodic Table of the Elements, preferably a metal atom of Group 4, 5 or 6, more preferably a metal atom of 4. groups of the Periodic Table of the Elements, most preferably a zirconium, titanium or hafnium atom;

X are leaving groups which may be the same or different, preferably anionic leaving groups, more preferably are independently selected from the group consisting of hydrogen, hydrocarbon

31925 / T er * C rffr 'r <, r r-rcfer, crrrrrrcr>. rtcrerrcrr c. , orrc <<. ' rr _crr .

a group, heteroatom or halogen atom, most preferably represent alkyl groups, y is 0 or 1 (if y is 0, then no L group is present), n is the oxidation state of the metal M, preferably +3, +4 or +5, more preferably +4, m is the formal charge of YZL or YZL, preferably 0, -1, -2 or -3, more preferably -2,

L is an element of the 15th or 16th group of the Periodic Table of the Elements, preferably a nitrogen atom,

L 1 is an element of a group 15 or 16 element or a group comprising an element of a group 14 element, preferably a carbon, silicon or germanium atom,

Y is an element of a Group 15 element, preferably a nitrogen or phosphorus atom, more preferably a nitrogen atom,

Z is a Group 15 element, preferably a nitrogen or phosphorus atom, more preferably a nitrogen atom,

R ¹ and R ² are independently selected from the group consisting of a hydrocarbon group containing from 1 to 20 carbon atoms, a heteroatom containing up to 20 carbon atoms, a silicon atom, a germanium atom, a tin atom, a lead atom or a phosphorus atom, preferably from the group comprising an alkyl group having from 2 to 20 carbon atoms, an aryl group or an arylalkyl group, more preferably from the group consisting of a linear, branched or cyclic alkyl group having from 2 to 20 carbon atoms, most preferably from the group comprising hydrocarbon groups having from 2 to 6 carbon atoms,

R ³ is absent or selected from the group consisting of a hydrocarbon group, a hydrogen atom, a halogen atom, a heteroatom-containing group, preferably a linear, cyclic or branched alkyl group having from 1 to 20 carbon atoms, more preferably not

31925 / T f rr r r r c r,

C r r C

C 6 -C 8 (R ⁸⁾ is R ³ present or selected from the group consisting of hydrogen and alkyl, most preferably is hydrogen,

R ⁴ and R ⁵ are independently selected from the group consisting of alkyl, aryl, substituted aryl, cyclic alkyl, substituted cyclic alkyl, cyclic arylalkyl, substituted cyclic arylalkyl, and a polycyclic system preferably containing up to 20 carbon atoms, more preferably from 3 to 10 carbon atoms, even more preferably from the group consisting of a hydrocarbon group having from 1 to 20 carbon atoms, an aryl group having from 1 to 20 carbon atoms, an arylalkyl group having from 1 to 20 carbon atoms, and a heteroatom containing group such as a group PR ₃ in which R represents an alkyl group, wherein R ¹ and R ² may be joined together and / or R ⁴ and R ⁵ may be joined together,

R ⁶ and R ⁷ are not independently present or are independently selected from the group consisting of hydrogen, alkyl, halogen, heteroatom, and hydrocarbon, preferably from the group consisting of linear, cyclic or branched alkyl groups containing from 1, up to 20 carbon atoms, more preferably these groups are absent, and

R * is either absent or selected from the group consisting of hydrogen, a group containing an atom of an element of the 14th group of the Periodic Table, a halogen atom and a group containing a heteroatom.

The term "formal charge of YZL or YZL" refers to the charge of the entire ligand in the absence of said metal and leaving groups X.

By the term "R ¹ and R ² may be joined together" it is understood that the groups R ¹ and R ² may be directly bonded to one another or may be bonded to each other through other groups. The term "R ⁴ and R ⁵ may be joined together"

31925 / T • e e e e r • c e

c. It is understood that the groups R ⁴ and R ⁵ can be directly bonded to one another or can be bonded to each other through other groups.

By alkyl is meant linear or branched alkyl groups or alkenyl groups, alkynyl groups, cycloalkyl groups or aryl groups, acyl groups, aroyl groups, alkoxy groups, aryloxy groups, alkylthio groups, dialkylamino groups, alkoxycarbonyl groups, aryloxycarbonyl groups, aryloxycarbonyl groups, aryloxycarbonyl groups, aryloxycarbonyl groups, alkyl- or dialkylcarbamoyl groups, acyloxy groups, acylamino groups, aroylamino groups, linear, branched or cyclic alkylene groups or combinations thereof. Arylalkyl means a substituted aryl.

In a preferred embodiment, the groups R ⁴ and R ⁵ independently of one another represent a group of the general formula 1:

R ⁸

R ⁹ (D

Binding to Z or Y where:

R ⁸ to R ¹² are independently selected from the group consisting of hydrogen, alkyl of 1 to 40 carbon atoms, halogen, heteroatom, heteroatom containing up to 40 carbon atoms, preferably linear or branched alkyl containing from 1 to 20 carbon atoms, preferably methyl, ethyl, propyl or butyl, or any two of R ⁸ to R ¹² may together

31925 / T

It is possible to form a cyclic group and / or a heterocyclic group, wherein said cyclic groups may be aromatic.

In a preferred embodiment of the present invention, the groups R ⁹ , R ¹⁰ and R ^{12 are} independently selected from the group consisting of methyl, ethyl, propyl or butyl (including all isomers). More preferably, R ⁹ , R ¹⁰ and R ^{12 are} methyl, and R ⁸ and R ¹¹ are hydrogen.

In a particularly preferred embodiment of the present invention, the groups R ⁴ and R ^{5 represent the} groups of formula 2:

Binding to Z or Y

In this embodiment, the group M represents an atom of an element of group 4 of the periodic table, preferably a zirconium, titanium or hafnium atom, more preferably a zirconium atom; L, Y and Z are each nitrogen; R ¹ and R ² are both -CH 2 -CH 2 -; R ³ represents a hydrogen atom; and R ⁶ and R ⁷ are absent.

In another preferred embodiment of the present invention, at least one X group is a substituted hydrocarbon group, preferably a substituted alkyl group containing more than. More preferably an aryl group substituted with an alkyl group. The most preferred aryl-substituted alkyl group is benzyl.

In a particularly preferred embodiment of the present invention, the structure of the metal-containing compound and the Group 15 element of the Periodic Table of the Elements can be represented by Formula A:

31925 / T e e r r p r r r c r c r r r r ** r c r,

(A)

In this formula, Ph refers to a phenyl group.

Metal compounds containing an element of the 15th element of the Periodic Table of the Elements are prepared by known methods, such as those described in published European Patent Application No. EP 0 893 454, US Patent No. 5,889,128 and reference materials cited in US Patent No. 5,889,128, the contents of which are incorporated herein by reference. U.S. Patent Application Ser. No. 09 / 312,878, filed May 17, 1999, discloses a gas phase or slurry polymerization process employing a supported supported bisamide catalyst, the disclosure of which is also incorporated herein by reference. reference material.

A preferred method of directly synthesizing these compounds comprises reacting a neutral ligand (see, for example, YZL or YZL in Formula I or II) with M ⁿ X _n , where M is a metal atom of Group 3-14, n is oxidizing the condition of the metal M and each of the groups X represents an anionic group, such as a halide, in a non-coordinating or weakly coordinating solvent such as ether, toluene, xylene, benzene, dichloromethane and / or hexane or another solvent having a boiling point above 60 ° C

31925 / T yr c - yr r. rrrrr - at a temperature of from about 20 ° C to about 150 ° C (preferably at a temperature of 20 ° C to 100 ° C), preferably for at least 24 hours, followed by reaction of the resulting mixture with an excess (such as four or more); with several equivalents) of an alkylating agent such as methylmagnesium bromide in ether. The resulting magnesium salts are removed from the mixture by filtration and the resulting metal complex is isolated by standard procedures.

In one embodiment of the present invention, a metal compound containing a Group 15 element atom is prepared by a process comprising reacting a neutral ligand (see, for example, YZL or YZL in Formula 1 or 2) with a compound of Formula M ⁿ X _n (wherein M is a metal atom of Group 3-14, n is the oxidation state of the metal M and each X represents an anionic leaving group) in a non-coordinating or weakly coordinating solvent at a temperature of about 20 ° C or higher, preferably at a temperature of about 20 ° C to about 100 ° C, followed by reacting the resulting mixture with an excess of alkylating agent and isolating the resulting metal complex. Preferably, the boiling point of the solvent is above 60 ° C, such as toluene, xylene, benzene and / or hexane. In another embodiment of the process, the solvent is ether and / or dichloromethane, the use of both solvents being preferred.

Metallocene compounds with sterically bulky ligand

In one embodiment of the present invention, the above-described metal compound comprising a Group 15 element may be combined with a second metal compound to form a mixed catalyst system. Said second metal compound is preferably a metallocene with a sterically bulky ligand.

Generally, the sterically bulky ligand metallocene group comprises semi and fully sandwich compounds containing one or more sterically bulky ligands that are bound to at least one metal atom. Typical sterile bulky ligand metallocene compounds are typically described as containing one or more sterically bulky

31925 / T e P rr r f, c Γ r e · c r e · 'r f, <· r p p <

1 'ligands and one or more leaving groups that are bound to at least one metal atom. In a preferred embodiment, at least one of said sterically bulky ligands is η-bound to said metal atom, most preferably η ⁵ -bound to said metal atom.

Sterically protected ligands are generally represented by one or more open, acyclic or fused ring groups or ring systems, or a combination thereof. These sterically bulky ligands, preferably said ring groups or ring systems, are usually composed of atoms of elements selected from Group 13-16 of the Periodic Table of the Elements, preferably atoms selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorus , germanium, boron and aluminum or combinations thereof. Most preferred are ring groups or ring systems composed of carbon atoms, such as cyclopentadienyl or cyclopentadienyl-type ligands or other ligands whose structure has similar properties to pentadiene, cyclooctatetradienyl or imide ligand. Said metal atom is preferably selected from the group of atoms of elements of groups 3 to 15 of the periodic table and from the group of lanthanides or actinoids. Preferably, said metal atom is a transition metal belonging to Groups 4-12 of the Periodic Table of the Elements, preferably belonging to Groups 4, 5 and 6 of the Periodic Table of Elements, and more preferably said transition metal is selected from Group 4 of the Periodic Table of Elements.

In one embodiment of the present invention, the structure of said sterically bulky ligand metallocene-based catalyst compound can be described by Formula III:

L ^A L ^B MQ _n (III) wherein:

M is a metal atom of Group 3-12 of the Periodic Table of the Elements or a group of lanthanides or actinoids. Preferably, a transition metal atom belonging to group 4, 5 or 6 of the Periodic Table of the Elements and yet

31925 / T r c e *?

more preferably the transition metal is selected from group 4 of the Periodic Table of the Elements, most preferably the metal is a zirconium, hafnium or titanium atom,

L ^a and l ^b are sterically bulky ligands which are open, acyclic or fused ring groups or ring systems, which ligands may be any auxiliary ligand systems which include unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, substituted cyclopentadienyl-type ligands heteroatom and / or cyclopentadienyl-type ligands containing a heteroatom.

Examples of sterically bulky ligands include cyclopentadienyl ligands, cyclopentaphenanthrenyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azenyl ligands, azenyl ligands, azenyl ligands, azenyl ligands, azenyl ligands, No. WO 99/40125), pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands, borobenzene ligands and the like, including but not limited to the hydrogenated versions of the above ligands, such as tetrahydroindenyl ligands. In an embodiment of the invention, groups ^1A and ^{1B may} represent any ligand structure which is capable of binding to the metal atom M by η-bond, preferably η ³ -bond, and most preferably η ^5- bond. In a further embodiment of the invention, the atomic molecular weight (MW) of the group L ^A or L ^{B is} higher than 60 atomic mass units (amu), preferably higher than 65 atomic mass units (amu). In another embodiment, L 1 ^A and L ^B may contain one or more heteroatoms such as nitrogen, silicon, boron, germanium, sulfur and phosphorus, in combination with carbon atoms, such that the atoms together form an open, acyclic or preferably condensed , a ring group or ring system, such as a heterocyclopentadienyl auxiliary ligand. Group of other sterically

The bulky ligands L ^A and L ^B include sterically bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, borrolides, porphyrins, phthalocyanines, corins, and other polyazamacrocyclic groups, without limitation to the examples. , Independently of one another can l_ of ^A and L ^B are the same or different type of bulky ligand that is bonded to the metal atom M. In one variant of the compound of formula III is present in only one of L ^A and ^B 1_.

Independently, the groups I- ^A and I- ^B may be unsubstituted or substituted by a combination of substituent groups R. Examples of substituent group R include one or more substituents selected from the group consisting of hydrogen, linear, branched alkyl or alkenyl, alkynyl, cycloalkyl or aryl, acyl, aroyl, alkoxy, aryloxy, alkylthiol, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- or dialkylcarbamoyl, acyloxy, a linearoylamino, acylamino, aylamino, acylamino, a group and combinations thereof, without being limited thereto. In a preferred embodiment of the present invention, the substituent groups R contain up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon atoms, which may also be substituted by halogens or heteroatoms and the like. Exemplary alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, or phenyl, and the like, without limitation, and including any optional isomers, such as tert-butyl, isopropyl, and the like. Other hydrocarbyl groups include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromhexyl, chlorobenzyl, and organometallic radicals substituted with hydrocarbyl groups, including trimethylsilyl, trimethylsilylmethyl, methylsilylmethyl, methylsilylmethyl, methylmethylsilyl, methylmethyl, methylsilyl,

31925 / T ft> e e ft Γ

Γ Γ

r. e β e <- ee ftft recrrer r. rcrrcr _r r ς · yy substituted halogenated hydrocarbon group, wherein the group comprising tris (trifluoromethyl) silyl, methyl-bis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like, disubstituted boron radicals including dimethylboron for example; and disubstituted pnictogen radicals including, such as, for example dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen-containing residues such as methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide. The group of non-hydrogen substituents R includes carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium and the like, including olefins such as olefinically unsaturated vinyl-terminated ligand-containing substituents such as but-3-enyl a group, a prop-2-enyl group, a hex-5-enyl group and the like, without being limited thereto. At least two R groups, preferably two adjacent R groups, are joined to form a ring structure containing from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron and combinations thereof. When R represents a group such as a 1-butanyl group, it may be attached to a M sigma metal atom by a carbon-based bond.

Other ligands, such as at least one leaving group Q, may be bonded to the metal atom M. In one embodiment of the present invention, the group Q is a monoionic labile ligand bound by sigma bond to the metal atom M. Depending on the oxidation state of the metal values of 0, 1 or 2, so that the above formula III shows a neutral metallocene-based catalyst compound with a sterically bulky ligand.

Examples of ligands that Q may represent include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals containing from 1 to 20 carbon atoms, hydrides or halogens and the like, or combinations thereof, without limitation the above examples. In another embodiment of the invention, two or more Q groups form part of a fused ring or ring system. As another example

31925 / T rr ♦ · f H cerrro · · · IP _FRR 'f' · e Γ R Λ R f rdq C '* C rr lu''cc t n' · _c p of Q ligands include those described above substituents of R, which includes cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, dimethyl, bis (N-methylanilide), bis (N-methylanilide), group and the like.

In one embodiment of the present invention, a group of metallocene-based catalytic compounds with a sterically bulky ligand comprises compounds of formula III in which groups I- ^A and I- ^B are joined together via at least one bridging group A, so that the structure of these compounds can be represented by formula IV:

LAL ^B MQ _n (IV)

The bridged structures of formula IV are known as metallocene-based catalyst compounds with a bridged, sterically bulky ligand. In this formula, the groups L ^A , L ^B , M and Q have the same meaning as in the general formula I. An example of a bridging group A is bridging groups containing at least one atom of the 13th to 16th group of the Periodic Table of the Elements, often referred to as as divalent groups such as at least one atom selected from the group consisting of carbon atom, oxygen atom, nitrogen atom, silicon atom, aluminum atom, boron atom, germanium and tin atom and combinations thereof, without limitation to the examples given. Preferably the bridging group A contains a carbon atom, a silicon atom or a germanium atom, more preferably the group A contains at least one silicon atom or at least one carbon atom. The bridging group A may also contain substituent groups R; as defined above, including halogen atoms and an iron atom. An example of a bridging group A includes, but is not limited to, compounds of the formulas R 1 C, R ₁ Si, R 1 Si R 1 Si, R 1 Ge, R 1 P, wherein the R 1 groups are independently selected from the group including a hydride group, a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, an organometallic group substituted with a hydrocarbon group

31925 / T e · f r · c r

Th e r c r c e e (

C <<* C Γ r

The organometallic group substituted with a halogenated hydrocarbon group, a disubstituted boron atom, a disubstituted atom of the pectide group, a substituted atom of the chalcogen group and a halogen atom or two R 'groups may be joined to form a ring or ring system. In one embodiment of the present invention, said bridged sterically bulky ligand metallocene catalyst compounds of formula (IV) contain two or more bridging groups A (see European Patent No. EP 664 301).

In another embodiment of the invention, the sterically bulky ligand metallocene-based catalyst compounds are those wherein the R substituents of the sterically bulky ligands L ^A and L ^B in formulas III and IV are substituted by the same or different number of substituents. In a further embodiment, said sterically bulky ligands L ^A and L ^B in formulas III and IV are different from each other.

Other sterile bulk ligand metallocene catalyst compounds and catalyst systems suitable for use in the present invention may include the catalyst compounds and catalyst systems disclosed in U.S. Patent Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, U.S. Pat. No. 5,239,022, U.S. Pat. No. 5,276,208, U.S. Pat. No. 5,296,434, U.S. Pat. No. 5,321,106, U.S. Pat. No. 5,329,031, U.S. Pat. No. 5,304,614, U.S. Pat. No. 5,677,401, U.S. Pat. No. 5,753,578, U.S. Pat. No. 5,854,363; International Application Nos. WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144, WO 98/41530, WO / 41529, WO 98/46650, WO 99/02540 and WO 99/14221 and published European patent applications, respectively. EP 0 578 838, EP 0 638 595, EP 0 513 380, EP 0 816 372, EP 0 839 834, EP 0 632 819, EP 0 739 361, EP 748 821 and EP 0 757 996, the contents of all of these documents is incorporated herein by reference.

In another embodiment of the present invention, a group of catalytic compounds based on sterically bulky ligand metallocenes which are

31925 / T

r. Suitable for use according to the invention, heteroatom-bridged metallocene compounds containing one sterically bulky ligand. These types of catalysts and catalyst systems have been described, for example, in International Publication Nos. WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO 96/00244, WO 97/15602 and WO 99/20637; US 5,057,475, US 5,096,867, US 5,055,438, US 5,198,401, US 5,227,440 and US 5,264,405, and European Patent Application Publication No. EP 0 420 436, all of which are incorporated herein by reference.

According to this embodiment of the present invention, the structure of the sterically bulky ligand metallocene-based catalyst compound can be described by Formula V:

L ^c AJMQ _n (V) where:

M is a metal of group 3 to 16 of the Periodic Table or a metal of the group of lanthanides or actinoids. Preferably, a transition metal atom of Group 4-12, more preferably transition group 4, 5 or 6 and even more preferably transition metal selected from Group 4 in any oxidation state, most preferably a titanium atom,

L ^c is a substituted or unsubstituted sterically bulky ligand bound to metal M,

J is a group bound to metal M and represents a heteroatom-containing auxiliary ligand,

A is a group bound simultaneously to metal M and group J and represents a bridging group,

Q is a monovalent anionic ligand, and n is an integer of 0, 1 or 2.

31925 / T e e * * e r c c r r, f C r · r

Γ C n n

In this embodiment, the group L ^c in formula V forms L ^c , A and J a fused ring system. In this embodiment, the groups L ' ^A , A, M and Q in formula V have the same meaning as in formula III.

In formula (V), J is a heteroatom-containing ligand in which J is an element with a coordination number of 3 selected from group 15 of the periodic group of elements or an element of group 16 of the periodic group of which has a coordination number of 2. In a preferred embodiment J contains a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, most preferably it contains a nitrogen atom.

In another embodiment of the present invention, the sterically bulky ligand metallocene-based catalyst compounds can be heterocyclic ligand complexes in which the sterically bulky ligands, which are formed by one or more rings or ring systems, contain one or more heteroatoms or combinations thereof. Examples of suitable heteroatoms include those from Group 13-16, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus, and tin, without being limited thereto. Specific examples of such catalytic compounds based on sterically bulky ligand metallocenes have been described in published international applications WO 96/33202, WO 96/34021, WO 97/17379, WO 98/22486, in European patent application number EP 0 874 005 and in patents US 5,637,660, US 5,539,124, US 5,554,775, US 5,756,611, US 5,233,049, US 5,744,417 and US 5,856,258, the contents of which are incorporated herein by reference.

In another embodiment of the present invention, said metallocene-based catalyst compounds with sterically bulky ligand complexes are known as catalysts based on a transition metal compound and bidentate ligands containing pyridine or quinoline groups such as those described in U.S. Patent Application No. USSN No. 09 / 103,620, filed June 23, 1998, the contents of which are incorporated herein by reference. In a further embodiment of this

31925 / T • · β β • · β η • e f β β

P r. <

of the invention, said metallocene-based catalysts with sterically bulky ligand complexes are disclosed in International Publication Nos. WO 99/01481 and WO 98/42664, the contents of which are incorporated herein by reference.

According to another embodiment of the invention, said metallocene-based catalyst compound with a sterically bulky ligand may be a metal complex, preferably a transition metal, a sterically bulky ligand, preferably a substituted or unsubstituted η-linked ligand, and one or more heteroalyl groups such as those described in the United States patents U.S. Patent Nos. 5,527,752 and 5,747,406; and European Patent No. EP 0 735 057, the contents of which are incorporated herein by reference.

It is also contemplated that any of the bulky ligand metallocene-based catalyst compounds of the present invention comprises at least one fluoride or fluorine-containing leaving group as described in U.S. Patent Application Serial No. 09 / 19.1,916, filed on Jun. November 1998.

In another embodiment, the other metal compound or second metal compound of the present invention is a sterically bulky ligand metallocene catalyst compound whose structure can be described by Formula VI:

L ^D MQ ₂ (YZ) X _n (VI) wherein:

T I t

M is a Group 3 to 16 metal atom, preferably a Group 4 to 12 transition metal atom, more preferably a Group 4, 5 or 6 transition metal group,

L ^d sterically bulky ligand bound to metal M, a

Q are all independently bonded to metal M,

31925 / T r r c ft r r r e r r r r r <p r r f C r- r; r t 'r r.

c yy yy P, i f

Q ₂ (YZ) forms a single-charge polydentate ligand,

A or Q represents a monovalent anionic ligand which is also bound to the metal M,

X is a monovalent anionic group when n equals 2 or a divalent anionic group when n equals 1, n is 1 or 2.

In formula VI, groups L and M have the same meaning as similar groups in formula III. The group Q has the same meaning as a similar group in formula III, preferably the group Q is selected from the group consisting of -O-, -NR-, -CR ₂ - and -S-; Y represents either a carbon atom or a sulfur atom; Z is selected from the group consisting of -OR, -NR ₂ , -CR ₃ , SR, -SiR ₃ , -PR ₂ , hydrogen, and substituted or unsubstituted aryl groups, provided that when Q is a group -NR- then Z is selected from the group consisting of -OR, -NR _2, -SR, -SiR _3, -PR ₂ radical and a hydrogen atom; R is selected from the group consisting of carbon, silicon, nitrogen, oxygen and / or phosphorus, preferably R is a hydrocarbon group containing from 1 to 20 carbon atoms, more preferably an alkyl group, a cycloalkyl group or an aryl group; n is an integer from 1 to 4, preferably 1 or 2; X is a monovalent anionic group when n is equal to 2 or X is a divalent anionic group when n is equal to 1; preferably X represents the carbamate group, carboxylate group, or other heteroalkyl group described by the combination of Q, Y, and Z groups.

In a particularly preferred embodiment of the present invention, said sterically bulky ligand metallocene compound is a compound of the formula:

31925 / T • • eccf ch ch ₃ // © Λ

H ₃ C-

C

H ₃ C-C ₃

CH3 ch ₃

In the catalyst system of the present invention, the above-described first and second metal compounds are mixed together in a molar ratio of from 1: 1000 to 1000: 1, preferably from 1: 99 to 99: 1, more preferably from 10: 90 to 90: 10, even more preferably in a ratio of 20: 80 to 80: 20, more preferably in a ratio of 30: 70 to 70: 30 and most preferably in a ratio of 40: 60 to 60: 40. The particular ratio of the individual compounds selected depends on the desired properties of the final product and / or the activation method.

Activating agent and methods of activation

The metal compounds described above are usually activated in various ways to form a catalyst compound having an empty coordination site at which one or more olefins are coordinated, inserted and polymerized.

For the purposes of the present invention, the term "activator" or "activating agent" refers to any compound or component or method by which any of the above-described metal compounds containing an element of Group 15 element and / or said catalyst compound can be activated to metallocene bases with sterically bulky ligand. Examples of activating agents include Lewis acid or a non-coordinating ionic activator or ionizing activator, or any other compound whose group

31925 / T r e r r y r y r f err c y r y r · · »f e c. r <·. r * r e- r r c, r

C rrcr r. · R, ς - rrrtrrrrcpr · r- rr> C · ^R f · r including Lewis bases, aluminum alkyl, commonly used types of cocatalysts and combinations thereof that can convert a neutral catalyst compound to the metallocene based bulky ligand or compound a metal containing an element of the 15th element of the Periodic Table of Elements to a catalytically active metal compound containing an element of the 15th group of the Periodic Table of Elements, respectively; to a catalytically active metallocene cation with a sterically bulky ligand. The present invention also includes the use of an alumoxane or modified alumoxane as an activating agent and / or the use of ionizing activating agents, either neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, trisperfluorophenylboron organometallic precursor or trisperlfluorobluor a precursor, polyhalogenated heteroborane anions (see published international application number WO 98/43983) or combinations thereof capable of ionizing a neutral sterile bulky ligand metalocene catalyst compound and / or a metal compound containing a Group 15 element atom elements of the present invention.

In one embodiment of the present invention, an activation method may be used in which ionic compounds without active proton are used but which are capable of producing as a catalytic cation a metal compound containing a Group 15 element or a sterically bulky metallocene catalytic cation ligand, such a non-coordinating anion. Such compounds have been described in published European patent applications EP 0 426 637, EP 0 573 403 and in US Patent No. 5,387,568, the contents of which are incorporated herein by reference.

There are many processes for the preparation of alumoxane and modified alumoxanes, and a specific example of such a process is disclosed in U.S. Patent Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, No. 4,968,827, US 5,308,815, US

31925 / T r r r * ϊ c p r r π c r r p c i pr 'i

5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, and 5,856,346; EP 0 561 476, EP 0 594 218, European Patent Nos. EP 0 279 586 and EP 0 586 665, and International Publication No. WO 94/10180, without limitation to the examples given, the contents of all the above-mentioned documents being incorporated herein as reference material.

The organoaluminum compounds used as activating agents of the present invention include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-oxyl aluminum, tri-n-octyl aluminum, and the like.

The ionizing compounds may contain active hydrogen or any other cation that is associated but not coordinated or only weakly coordinated with the remaining ion of said ionizing compound. Such compounds and the like have been described in published European patent applications EP 0 570 982, EP 0 520 732, EP 0 495 375, EP 0 277 003 and EP 0 277 004, EP 0 500 944, U.S. Pat. US 5,153,157, US 5,198,401, US 5,066,741, US 5,206,197, US 5,241,025, US 5,384,299 and US 5,502,124, and US Patent Application Serial No. USSN 08 / 285,380, filed Aug. 3, 1994, the contents of all documents cited hereinabove. included as reference.

Other activating agents include those disclosed in International Publication Number WO 98/07515, the contents of which are incorporated herein by reference, exemplified by tris (2,2 ', 2-nonafluorobiphenyl) fluoroaluminate. The present invention also encompasses the use of mixtures of activating agents such as mixtures of alumoxanes and ionizing activating agents, as described, for example, in European Patent No. EP 0 573 120, in published International Applications Nos. WO 94/07928 and WO 95/14044, and in United States patents. US 5,153,157 and US 5,453,410, all of which are incorporated herein by reference

31925 / T e c c t c r r * C C C c c C r r r * * * týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto týchto WO 98/09996, the disclosure of which is incorporated herein by reference, describes the activation of catalyst compounds by perchlorates, periodates, including hydrates thereof. International Publication Nos. WO 98/30602 and WO 98/30603, the contents of which are incorporated herein by reference, have described the use of lithium (2,2'-bisphenyiditrimethylsilicate) with 4 molecules of THF as the catalyst compound activator. WO 98/18135, the contents of which are incorporated herein by reference, have described the use of organoboron-aluminum activating agents. EP 0 781 299 discloses the use of a silylium salt in combination with a non-coordinating compatible anion. Other activation methods, such as the use of radiation, can also be used to convert a neutral catalyst compound or precursor into a catalytic cation by which olefins can be polymerized (cf. EP 0 615 981, the contents of which are incorporated herein by reference) , electrochemical oxidation and the like. Other activating agents or methods for activating the catalyst compounds have been described, for example, in U.S. Patent Nos. 5,849,852, 5,859,653 and 5,869,723, and in International Publication Nos. WO 98/32775 and WO 99/42467 (dioctadecylmethylammoniumumbis (tris) pentafluorophenyl) ), the contents of which are incorporated herein by reference.

In one embodiment of the present invention, said activating agent is a Lewis acid, more preferably an aluminum-based Lewis acid, even more preferably a neutral aluminum-based Lewis acid, comprising at least one, preferably two, halogenated aryl ligands and one or two other non-halogenated mono-ionic ligands. aryl ligands. The class of Lewis acids used in this embodiment includes aluminum-based Lewis acids that contain at least one sterically bulky, electron-acceptor auxiliary ligand, such as a halogenated aryl ligand contained in tris (perfluorophenyl) boron or

31925 / T r.

· T e pi pi pi pi pi pi pi r pi tris (perfluoraphthyl) borane. These sterically bulky auxiliary ligands are those which are sufficient to allow said Lewis acids to function as electronically stabilizing, compatible, non-coordinating anions. Stable ionic complexes are formed when said anions are not suitable ligands for strong Lewis acids, which in this case are transition metal cations containing a group 15 element of the Periodic Table of the Elements used in the advertising polymerization, i. by preventing the transfer of the ligand, which would lead to the neutralization of said cations and thus to their deactivation due to the ongoing polymerization.

The Lewis acids meeting the above description of the preferred activating agent of the present invention can be described by the following formula (VII):

R @ ₁ Al (ArHal) ₃ . _n (VII) where:

R is a mono-anionic ligand,

ArHal is a halogenated aromatic group having 6 carbon atoms or a polycyclic aromatic group having a higher number of carbon atoms or a group containing aromatic rings in which two or more rings (or fused ring systems) are attached directly to each other and n is 1 to 2, preferably 1 .

In another embodiment, at least one group (ArHal) of formula VII is a halogenated aromatic group containing at least 9 carbon atoms, preferably a fluorinated naphthyl group. Suitable R ligands include a substituted or unsubstituted aliphatic or aromatic hydrocarbon group containing from 1 to 20 carbon atoms, wherein the term substituted means that at least one hydrogen atom attached to the carbon atom of the group is replaced by a hydrocarbon group, halide, halogenated hydrocarbon group or organometallic group. a group containing a hydrocarbon or halogenated hydrocarbon group,

31925 / T r * r r r r r r r r r r r r <: r r r r CC <* C rt. [- - rr rr r r r r r r r r r ·. »R c - 'C. r ·.

dialkylamido, alkoxy, siloxy, aryloxy, alkylsulfido, arylsulfido, alkylphosphido or other anionic substituents; fluoride; sterically bulky alkoxides, the term sterically bulky in this context means a hydrocarbon group containing at least 4 carbon atoms, for example up to 20 carbon atoms, such as tert-butoxide, 2,6-dimethylphenoxide, 2,6-di (tert-butyl) a phenoxide group; -SR, -NR ₂ , -PR 2, wherein R is independently selected from the group consisting of substituted or unsubstituted hydrocarbon as defined above; and an organometallic group containing a hydrocarbon group having from 1 to 30 carbon atoms, such as a trimethylsilyl group, without being limited thereto.

Particular examples of the group ArHal include phenyl, naphthyl and anthracenyl according to U.S. Patent No. 5,198,401 and halogenated biphenyl groups according to International Publication No. WO 97/29845. For the purposes of the present invention, halogenated or halogenated, it is understood that at least one third of the hydrogen atoms bound to the carbon atoms that form the aryl-substituted aromatic ligands are replaced by halogenated atoms, and more preferably said aromatic ligands are perhalogenated. The most preferred halogen of the present invention is fluorine.

According to another embodiment of the present invention, the molar ratio of metal from the activator component to the metal component of the catalytic metal compound comprising a Group 15 element supported on a suitable support is in the range of 0.3: 1 to 1000: 1, preferably in the range of from 20: 1 to 800: 1, and more preferably in the range of from 50: 1 to 500: 1. When said activating agent is an ionizing activator, such as tetrakis (pentafluorophenyl) boron anionic activators, the molar ratio of metal in this an activator component to a metal component of a catalytic metal compound comprising a Group 15 element of the Periodic Table of the Elements from 0.3: 1 to 3: 1.

31925 / T

C Γ.

f c r Γ r r ς

C r ·· c r r i 'c r ‘r r y r

C r '· r c · * r <ς

In a further embodiment of the present invention, the above-described metal catalyst compounds comprising a Group 15 element atom and / or the above-described sterically bulky ligand metallocene-based catalyst compound may be combined with one or more of the catalyst compounds of formulas III-VI and one or a plurality of activators or activation methods described above.

In another method of forming the mixed catalyst composition of the present invention, the modified alumoxanes are mixed with the first and second metal compounds of the present invention to form a catalyst system. In another embodiment, MMA03A (which is a modified methylalumoxane in heptane, commercially available from Akzo Chemicals, Inc., the Netherlands under the trade name Modified Methylalumoxan type 3A) is stirred, see, for example, examples of such aluminoxanes described in U.S. Patent No. 5,041,584, the contents of which are incorporated herein by reference) with said first and second metal compounds to form a catalyst system.

In a particular embodiment of the present invention, when compounds of the metals of formulas 1 and 2 are used which are both activated by the same activating agent, the content of the individual compounds, expressed as a percentage by weight based on the total weight of both compounds, is preferred. from 10 to 95% by weight of the compound of formula 1 and from 5 to 90% by weight of the compound of formula 2, preferably from 50 to 90% by weight of the compound of formula 1 and from 10 to 50% by weight of the compound of formula 2 1 and from 40 to 20 weight percent of the compound of formula 2. In a particularly preferred embodiment, the compound of formula 2 is activated with methylalumoxane, mixed with the compound of formula 2 and injected into the reactor.

In another particular embodiment of the present invention, wherein a compound of Formula I and an indenyl zirconium trispivalate are used, both of which are activated by the same activating agent, the preferred content is

31925 / T r r r r «? yyyy yyyyy yyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy

%, based on the total weight of the two catalysts excluding the weight of the activating agent and the carrier, from 10 to 95% by weight of the compound of the formula I and from 5 to 90% by weight, preferably from 50 to 90% by weight And from 10 to 50% by weight of indenyl zirconium trisivalate, more preferably from 60 to 80% by weight of a compound of formula I and from 40 to 20% by weight of indenylzirconium trispivalate. In a particularly preferred embodiment, the indenyl zirconium trispivalate is activated with methylalumoxane, mixed with a compound of formula I and injected into the reactor.

Generally, the metal compounds of the present invention are mixed with the activating agent in ratios of from about 1000: 1 to about 0.5: 1. Preferably, the metal compounds of the present invention are mixed with the activating agent in a ratio of about 300: 1 to about 1: 1. About 1: 1, preferably from about 150: 1 to about 1: 1, when borates, borates, aluminates, etc. are used. preferably said ratio is from about 1: 1 to about 10: 1, and in the case of the use of alkyl aluminum compounds (such as diethylaluminum chloride in admixture with water), said ratio is preferably from about 0.5: 1 to about 10: 1.

Conventional catalyst systems

The mixed catalyst composition of the present invention may optionally comprise a metal compound as described above comprising a Group 15 element of the Periodic Table of the Elements and a conventional transition metal catalyst. '<

Conventional transition metal catalysts include Ziegler-Natta catalysts, vanadium catalysts, and Phillips catalysts, which are well known to those skilled in the art. Examples of Ziegler-Natta catalysts are described in Ziegler-Natta Catalysts and Polymerizations, John Boor, Academic Press, New York, 1979. Examples of conventional transition metal catalysts are also described in U.S. Patent Nos. 4,115,639, 4,077,904, U.S. Pat.

31925 / T o r e r e a e n e c n r r r <

CC r c

US 4,482,687, US 4,564,605, US 4,721,763, US 4,879,359, US 4,960,741, the contents of which are incorporated herein by reference. Conventional transition metal catalyst compounds which can be used according to the present invention comprise transition metals from Groups 3 to 17 of the Periodic Table of the Elements, more preferably from Groups 4 to 12 of the Periodic Table of the Elements, more preferably from Groups 4 to 6 of the Periodic Table. elements.

The structure of these conventional transition metal catalysts can be represented by the general formula:

MR _X where:

M is a metal atom of Group 3 to 17 of the Periodic Table of the Elements, preferably z

Groups 4 to 6 of the Periodic Table of the Elements, preferably from group 4 of the Periodic Table of the Elements, most preferably titanium;

R is halogen or oxycarbon, and x is the oxidation state of metal M.

Particular examples of the group R include, but are not limited to, alkoxy, phenoxy, bromide, chloride, and fluoride. Ako k

a specific example of a conventional catalyst, a transition metal, wherein M is titanium, may include TiCl _4, TiBr ₄₎ Ti (OC 2 H ₅₎ 3 Cl, Ti (OC ₂ H ₅₎ Cl _3, Ti (OC ₄ H _{9) 3} Cl Ti (OC ₃ H ₇ ) ₂ CI ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , TiCl ₃ .1 / 3 AlCl ₃ and Ti (OC-1 ₂ H ₂ 5) CI ₃ , without limitation to these examples .

Conventional electron donor complexes of magnesium / titanium electron donor complexes which can be used according to the present invention have been described, for example, in U.S. Patent Nos. 4,302,565 and 4,302,566, the contents of which are incorporated herein by reference. MgTiCl ₆ (ethyl acetate) _{4 is} particularly preferably used.

GB 2,105,355 and US 5,317,036, the contents of which are incorporated herein by reference, disclose various conventional catalyst compounds.

31925ΛΓ r r r ς r. r r e r- c c c r. r <· c

C rrfrccrfercrrrcrc cc - r .c vanadium. Examples of a conventional vanadium catalyst compound include vanadyl trihalide, vanadylalkoxy halides and vanadylalkoxides such as VOCl ₃ , VOCl 2 (OBu), where Bu is butyl and VO (OC ₂ H 5) ₃ ; vanadium tetrachloride and vanadium alkoxy halides such as VCI ₄ and VCI ₃ (OBu), vanadium and vanadylacetoacetonates and chloroacetyl acetonates such as V (AcAc) ₃ and VOCl ₂ (AcAc) wherein (AcAc) is an acetylacetonate group, without being limited thereto. Preferred conventional vanadium catalyst compounds include VOCl ₃ , VCl ₄ and VOCl ₂ -OR, wherein R is a hydrocarbon radical, preferably an aliphatic or aromatic hydrocarbon radical containing from 1 to 10 carbon atoms such as ethyl, phenyl, isopropyl, butyl a propyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, a naphthyl group, etc., and vanadium acetoacetonates.

A group of conventional chromium catalyst compounds, often referred to as Phillips catalysts suitable for use in the present invention, include CrO ₃ , chromocene, silylchromate, chromyl chloride (CrO ₂ Cl ₂ ), chromium-2-ethylhexanoate, chromoacetyl acetonate (Cr (3). AcAc) _3), and the like. Non-limiting examples of these catalysts are described in U.S. Patent Nos. 3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, the contents of which are incorporated herein by reference.

Other conventional transition metal catalyst compounds and catalyst systems suitable for use in the present invention have been described in U.S. Patent Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062, 4,379,758, 5,066,737, 5,763,723, 5,849,655 , US 5,852,144, US 5,854,164 and US 5,869,585, and in published European patent applications EP 0 416 815 and EP 0 420 436, the contents of which are incorporated herein by reference.

Other catalysts may include cationic catalysts such as AlCl ₃ , and other well known cobalt, iron, nickel, and palladium catalysts. See, for example, U.S. Patent Nos. 3,487,112, U.S. Pat

31925 / T

C C f. r r 'r r r.

Γ r i * Z ^RL Γ rrr PP frrrrrr r> fr

OC yyyy yyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy

No. 4,472,559, US 4,182,814 and US 4,689,437, the contents of which are incorporated herein by reference.

Typically, these conventional transition metal catalyst compounds, with the exception of some conventional chromium catalyst compounds, are activated by one or more of the conventional cocatalysts described below. Conventional transition metal catalysts can also be activated by the above activating agents, as will be apparent to those skilled in the art.

The structure of conventional cocatalysts for use with the conventional transition metal catalyst compounds described above may be described by the general formula:

M ³ M ⁴ vX ² cR ³ bc where:

M ³ is a metal atom from Groups 1 to 3 and 12 to 13 of the Periodic Table of the Elements,

M ⁴ is a metal atom of Group 1 of the Periodic Table of Elements, v is a number from 0 to 1,

X ² is a halogen atom, c is a number from 0 to 3,

R ^{3 is a} monovalent hydrocarbon radical or a hydrogen atom, b is a number from 1 to 4, wherein the difference bc is at least 1.

Structure of other conventional organometallic cocatalysts at

the use together with the conventional transition metal catalyst compounds described above can be described by the general formula:

M ³ R ³ k where:

M ³ is the metal of IA, HA, IIB or IIIA of the Periodic Table of the Elements, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium and gallium,

31925 / T e c c e e c * e f

9 e e e f c 9

- cr; crr p p β C 9 r Γ rr C ·· P Γ k is equal to 1, 2 or 3, according to the valency of the metal M ³ , which itself depends on the particular group to which the metal M ³ belongs,

R ³ may be a monovalent hydrocarbon radical.

As an example of conventional organometallic cocatalysts for use

Along with the conventional catalyst compounds described above, mention may be made of methyl lithium, butyl lithium, dihexyl mercury, butyl magnesium, diethylcadmium, benzyl potassium, diethylzinc, tri-n-butyl aluminum, diisobutylethyl boron, diethylcadmium, di-n-butyl amine, tri-n-butylzinc but not limited to trihexyl aluminum, triethyl aluminum, trimethyl aluminum and triisobutyl aluminum. Other conventional cocatalysts include Group 2 monoorganohalides and metal hydrides and Group 3 and 13 metal monohydrides and metal hydrides. A representative of this type of conventional co-catalyst are diisobutylaluminum bromide, isobutylboron dichloride, methyl magnesium chloride, etylberýliumchlorid, etylkalcium bromide, diisobutylaluminum hydride, methylcadmium, dietylbóriumhydrid, hexylberyllium, dipropylbóriumhydrid, oktylmagnéziuhnhydrid, butylzinkum anhydride, dichlórbóriumhydrid, dibrómalumíniumhydrid and brómkadmiumhydrid, not limited to these examples. Conventional organometallic cocatalytic compounds are well known to those skilled in the art and are discussed in more detail in U.S. Patent Nos. 3,221,002 and 5,093,415, the contents of which are incorporated herein by reference.

Carriers and general application methods

The above catalyst compounds comprising a Group 15 element and a mixed catalyst system of the present invention comprising a catalyst compound comprising a Group 15 element and a sterically bulky ligand metallocene catalyst or a conventional catalyst compound may be used. combined with one or more support materials or carriers using coating methods well known in the art of catalyst manufacture and described below. For example, in one of

31925 / T e e f e »« c »0 f>

r r e o r f

r. In a possible embodiment of the present invention, a catalyst compound comprising a Group 15 element or a mixed catalyst system of the present invention is used together with a suitable carrier, wherein the catalyst compound or mixed catalyst system can be deposited on, for example, a supported catalyst. contacted, may be steamed onto the support (i.e., vapor deposited), bound to the support, introduced into the support, adsorbed to the surface of the support or absorbed into or onto the support. Also encompassed by the present invention is the use of a mixed metal system wherein said sterile bulk ligand metallocene catalyst is supported on a different carrier from a compound comprising a Group 15 element. This arrangement is mainly used in the case of polymerization taking place in several reactors, where one reactor uses a supported catalyst system for the production of a high molecular weight component and the second reactor uses a second catalyst system for the production of a low molecular weight component. in a suitable carrier.

The terms "carrier" or "carrier" are used interchangeably and are meant to include any carrier material, preferably a porous carrier material, including inorganic and organic carrier materials. Examples of inorganic carrier materials are inorganic oxides and inorganic chlorides. Other carriers include polymeric carrier materials such as polystyrene, functionalized or crosslinked organic carrier materials such as polystyrene-divinylbenzene polyolefins, polymerization compounds or any other organic or inorganic carrier material and the like, and mixtures thereof, without limitation to these examples.

Preferred carriers are inorganic oxides, the group comprising metal oxides from Groups 2, 3, 4, 5, 13 and 14 of the Periodic Table of the Elements. Preferred carriers include silica, alumina, silica alumina, and mixtures thereof. Other carriers useful in the present invention include magnesium oxide, titanium dioxide, zirconia, chloride

31925 / T r r f r r f r r p r e r f magnesium, montmorillonite (see European Patent No. EP 0 511 665), phyllosilicate, zeolites, talc, clays and the like. Further, according to the present invention, it is also possible to use mixtures of said support materials, such as chromium-containing silica, alumina-silica, silica-titanium dioxide and the like. Other carrier materials can be, for example, the porous acrylate polymers described in European Patent No. EP 0 767 184, the contents of which are incorporated herein by reference.

According to the present invention, it is preferred that the carrier, most preferably the inorganic oxide, has a surface area in the range of about 10 m ² / gram to about 100 m ² / gram, a pore volume in the range of about 0.1 cm ³ / gram to about 4 0 cm ³ / gram and a mean particle size ranging from about 5 µm to about 500 µm. More preferably, the surface area of the carrier of the present invention is in the range of about 50 m ² / gram to about 500 m ² / gram, the pore volume of the carrier is in the range of about 0.5 cm ³ / gram to about 3.5 cm ³ / gram and the mean particle size of the carrier is in the range of about 10 µm to about 200 µm. Even more preferably, the surface area of the carrier of the present invention is in the range of about 100 m ² / gram to about 400 m ² / gram, the pore volume of the carrier is in the range of about 0.8 cm ³ / gram to about 5.0 cm ³ / and the mean particle size of the carrier is in the range of about 5 µm to about 100 µm. The mean pore size of the carrier of the invention is typically in the range of from about 10 angstroms to about 1000 angstroms, preferably from about 50 angstroms to about 500 angstroms, and more preferably from about 75 angstroms to about 450 angstroms.

Examples of methods for applying catalysts to carriers that can be used in the present invention are described in U.S. Patent Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766 5,468,702

5,529,965, US 5,554,704, US 5,629,253, US 5,639,835, US 5,625,015, US

5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400

5,723,402, US 5,731,261, US 5,759,940, US 5,767,032, US 5,770,664, US

31925 / T

Nos. 5,846,895 and 5,939,348, and US Patent Application Nos. USSN 271,598, filed July 7, 1994 and USSN 788,736, filed January 23, 1997, International Publication Nos. WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297 and in European patent number EP 0 685 494, the contents of which are incorporated herein by reference.

Many other methods are known which can be used to apply the polymerization catalysts or mixed catalyst systems of the present invention to a suitable support. For example, hafnium compounds containing a Group 15 element and / or a mixed catalyst system of the present invention that includes sterically bulky ligand metallocene catalyst compounds may contain a polymer-bound ligand as described in the United States patents Nos. 5,473,202 and 5,770,755, the contents of which are incorporated herein by reference; hafnium compounds comprising a Group 15 element of the Periodic Table and / or the sterically bulky ligand metallocene-based catalyst compounds of the present invention may be spray dried as described in U.S. Patent No. 5,648,310, the contents of which are incorporated herein as reference material; the carrier material to be used in conjunction with hafnium compounds comprising a Group 15 element of the Periodic Table of the Elements and / or the sterically bulky ligand metallocene catalyst compounds of the present invention may be functionalized as described in published European patent application EP number No. 0,802,203, the contents of which are incorporated herein by reference, or at least one substituent or leaving group is selected from those described in U.S. Patent No. 5,688,880, the contents of which are incorporated herein by reference.

In another embodiment, the present invention relates to a catalyst system comprising a compound comprising a Group 15 element of the Periodic Table of the Elements and / or a mixed catalyst system comprising catalytic catalysts.

31925 / T • · f »r f f f f f f <<<<<<<<<<

sterically bulky ligand metallocene compounds comprising surface modifying agents for use in the production of a supported catalyst system according to International Publication Number WO 96/11960, the contents of which are incorporated herein by reference. The catalyst systems of the present invention can be prepared in the presence of an olefin such as 1-hexene.

In another embodiment, a catalyst system comprising a hafnium compound comprising a Group 15 element and a mixed catalyst system comprising a sterically bulky ligand metallocene catalyst compound of the invention may be combined with a metal-containing carboxylic acid salt such as, for example, aluminum carboxylates such as aluminum mono-, di- and tristearate, aluminum octoates, aluminum oleate and aluminum cyclohexylbutyrates as described in U.S. Patent Application Serial No. 09 / 113,213, filed July 10, 1998.

A method for depositing a compound-based catalyst system comprising a Group 15 element and / or a mixed sterile ligand metallocene-based catalyst system is described below and has also been described in U.S. Patent Application Serial Nos. USSN 265,533, filed on April 24, 1993. U.S. Patent 265,532, filed Jun. 24, 1994, and International Publication Nos. WO 96/00245 and WO 96/00243, the contents of which are incorporated herein by reference. In this method, a compound comprising a Group 15 element of the Periodic Table is used alone or together with a metallocene-based catalyst with a sterically bulky ligand. In this method, said catalyst compound or mixture of said catalyst compounds is suspended in a liquid to form a solution and a solution containing the activating agent and the liquid is prepared in a separate vessel. The liquid may be any compatible solvent or any other liquid that is capable of forming a solution or the like form of the catalyst compound or mixture of catalyst compounds and / or activator of the present invention. Most preferably said

31925 / T • 9 · e e r r r r r r e e r c c t r f r r «f- · · f.

In the method, the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene. Said solutions of the catalyst compound or mixture of catalyst compounds and activator are mixed together and added to the porous support material in such a ratio that the total volume of the solution of the catalyst compound or mixture of catalyst compounds and activator solution is less than four times the pore volume of the porous support material. a volume of less than 3 times the pore volume of the porous support material, more preferably less than twice the pore volume of the porous support material; wherein the preferred range of these volumes is in the range of from 1.1 to 3.5 times, and more preferably from 1.2 to 3 times.

Methods for measuring the total pore volume of a porous material are well known. Details of these methods are discussed in Experimental Methods in Catalytic Research, Vol. I, Academic Press, 1968 (specifically on pages 67-96). These preferred methods include the use of a conventional BET device to measure nitrogen absorption. Another well known method has been described in Innes, &quot; Total Porosity and Particle Density of Fluid Catalysts by Liquid Titration &quot;, Analytical Chemistry, 1956, 28, 332-334.

Other methods for applying the catalyst compounds of the present invention to a support material have been described in U.S. Patent Application Ser. No. 09 / 312,878, filed May 17, 1999, the contents of which are incorporated herein by reference.

When used in a mixed catalyst system, a catalyst compound comprising a Group 15 element of the present invention and a metallocene-based catalyst with a sterically bulky ligand is mixed in a molar ratio of from 1: 1,000 to 1,000: 1, preferably from 1; 99 to 99: 1, more preferably from 10: 90 to 90: 10, even more preferably from 20: 80 to 80: 20, more preferably from 30: 70 to 70: 30, and most preferably from 40: 60 to 60: 40.

In one embodiment of the blend system of the present invention, in particular using the system in polymerization

31925 / T r 'í r r. ; rfrrcceccrrr · c <42 in suspension, is the total deposited amount of a compound containing a Group 15 element and a sterically bulky ligand metallocene catalyst compound expressed in micromoles / gram of the resultant supported catalyst (this resulting catalyst). includes a carrier material, a catalyst mixture, and an activating agent), about 40 micromoles / gram, preferably about 38 micromoles / gram.

In another embodiment of the present invention, in particular gas phase polymerization using the blend system of the present invention, the total amount of compound containing a Group 15 element and a sterically bulky ligand metallocene catalyst compound is deposited. expressed in micromoles / gram of the resultant catalyst deposited on the support material (the resulting catalyst comprising support material, catalyst mixture and activating agent), less than 30 micromoles / gram, preferably less than 25 micromoles / gram, more preferably less than 20 micromoles / gram.

According to another embodiment of the invention, the R group of the above formula (VII) or a ligand contained therein may be covalently bonded to a support material, which is preferably a metal oxide or a metalloid or polymer. The Lewis base-containing carrier materials react with the Lewis acid activators to bind the Lewis acid to said carrier or to apply the activating agent to the carrier material, wherein one R group of formula R ₁ Al (ArHal) ₃ . _n is covalently bonded to said carrier material. For example, when the support material is silica, the Lewis base is the hydroxyl groups contained in the silica, and in this method of deposition of the activating agent it is the hydroxyl groups that bind to a single coordination site of said aluminum complex. In this embodiment of the invention the support material preferably a metal or metalloid oxide, preferably used such a support material having surface hydroxyl groups whose pK _a equal to or less than the _pK

31925 / T r. r r r r- r> r,

C Γ 'c. R '·· amorphous silica, i.e., pK _a of these hydroxyl groups is equal to or less than about 11th

Without being limited to any theory, it is believed that the covalently bound activating agent, which is a Lewis acid, first forms a dative

Also complexed with a silanol group contained, for example, in silica (this group behaves as a Lewis acid) to form a formal dipolar (zwitterionic) Bronsted acid which is bound to the metal / metalloid contained in the oxide that constitutes the carrier material . Apparently, the proton contained in said Brondsted acid protonates the R group contained in the Lewis acid, thereby cleaving it and covalently attaching the Lewis acid to the oxygen atom. Thus, the Lewis acid group R becomes a group R'-Ο- in which R 'is a suitable carrier material or substrate, for example silica or a polymerization carrier containing hydroxyl groups. Any carrier material that contains hydroxyl groups on its surface is suitable for use in this particular method of depositing a catalyst on a support. These beads also include glass beads.

In this embodiment, wherein the carrier material is a metal oxide composition, the compositions may further comprise oxides of other metals, such as aluminum, potassium, magnesium, sodium, silicon, titanium, and zirconium oxides, the compositions preferably being heat and / or or chemically treated to get rid of water and free oxygen. Such treatment is usually carried out under vacuum in a heated furnace, in a heated fluidized bed or with dehydrating agents such as organosilanes, siloxanes, alkyl aluminum compounds, etc. The rate of treatment should be such that most of the retained moisture and free oxygen are removed as far as possible, but a chemically significant amount of hydroxyl functionality is retained. Thus, for example, the support material can be annealed at a temperature of up to 800 ° C or even higher until it decomposes, and if a larger amount of anionic activating agent is to be applied to the support, it is convenient to anneal the support material for a shorter period of time. Unless stated

31925 / T r · ererrerrnr * r c. a silica with a metal oxide, it is usually desirable to deposit on the support from less than 0.1 millimole to 3.0 millimoles activator / gram SiO ₂ , which can be achieved, for example, by changing the annealing temperature of silica in the range of 200 ° C to 800 C. See Zhuralev et al., Langmuir, 1987, 3, 316 for a correlation between annealing temperature, annealing time and hydroxyl group content on the surface of silica particles.

Adjustment of the hydroxyl groups available as binding sites may also be accomplished by pretreatment prior to the addition of Lewis acid, with less than stoichiometric amounts of chemical dehydrating agents. These reagents are used in small amounts and each contain one ligand that is capable of reacting with silanol groups (such as (CH ₃ ) ₃ SiCl) or which is hydrolyzable in another way, minimizing interference with the reaction between the catalytic transition metal compound according to the invention. of the present invention and the bound activating agent. If the annealing temperature is less than 400 ° C, difunctional addition agents (such as (CH ₃ ) ₂ SiCl ₂ ) may be used to disconnect the pairs of hydrogen-bonded silanol groups present on the silica surface if annealing takes place under milder conditions. See, for example, Gorski et al., &Quot; Investigation of Quantitative SiOH Determination by the Silane Treatment of Disperse Silica &quot;, Journal of Colloid and Interface Science I, 1988, 126, 2 discussing the effect of silane addition agents on polymeric fillers based on the silica can also be used to modify the silanol groups on the surface of the catalyst support material of the present invention. Similarly, the use of a Lewis acid in greater than a stoichiometric amount required to react with the transition metal compounds of the present invention serves to neutralize excess silanol groups without significant detrimental impact on catalyst preparation and subsequent polymerization.

The polymeric carrier materials to be used according to the invention are preferably hydroxyl functional polymeric substrates.

31925 / T • f r - r ft t

However, such a functional group may also be selected from the group consisting of primary alkylamines, secondary alkylamines and other groups that are structurally incorporated into the polymer chain and are capable of acid-base reaction with the Lewis acid so that the ligand fills in the complex The aluminum one coordination site is protonated and replaced by a functional group that is part of said polymer. See, for example, functional group polymers described in U.S. Patent No. 5,288,677, the contents of which are incorporated herein by reference.

Other support materials suitable for use in the present invention include alumina, alumina, magnesium oxide, titanium dioxide, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays, chromium-containing silica, titanium dioxide silica and porous acrylate polymers.

In another embodiment of the present invention, one or more olefins, preferably one or more olefins containing from 2 to 30 carbon atoms or one or more alpha-olefins, preferably ethylene or propylene or mixtures thereof, are prepolymerized in the presence of a catalyst compound containing a metal compound before major polymerization. an element of group 15 of the periodic array of elements and / or metallocene-based catalysts with sterically bulky ligand, which are supported on a suitable support material. Said prepolymerization may be carried out batchwise (i.e. discontinuously) or continuously in gas phase, in solution or in suspension, including polymerization at elevated pressure. Said prepolymerization. may be carried out with any olefin monomer or mixture thereof and / or in the presence of any molecular weight regulating agent of the resulting polymer, such as hydrogen. Examples of prepolymerization processes are described in U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578, EP 0 279 863, and published international patent publication no.

31925 / T r r r r r r - r r r, r f.

e · r *. ·. r p r 7 · 7 C '* r r t. No. WO 97/44371, the contents of which are incorporated herein by reference.

Spraying a solution of a metal compound containing a Group 15 element (

In another embodiment of the present invention, the catalytic metal compound comprising a Group 15 element and an activating agent is fed to a slurry or gas phase polymerization reactor in a liquid carrier, preferably in the form of a solution. The catalyst and the activating agent of the present invention may be injected separately or together and may be mixed together immediately prior to the feed to the reactor or may be contacted together for a longer period prior to the feed to the reactor. Preferred liquid carriers include alkanes, preferably pentane, hexane, isopentane, toluene, cyclohexane, isopentane, heptane, octane, isohexane and the like. Particularly preferred liquid carriers are hexane, pentane, isopentane and toluene.

Said catalyst system, metal compounds and / or activating agent are preferably injected into the reactor in the form of one or more solutions. In one embodiment, a solution of activated metal compounds in an alkane such as pentane, hexane, toluene, isopentane and the like is fed to a slurry or gas phase reactor. According to another embodiment, said catalyst system or said components are injected into the reactor in the form of a suspension or an emulsion. In another embodiment, the transition metal compound of the present invention is contacted with an activating agent, such as modified methylalumoxane, in a solvent just before the solution is injected into the gas phase polymer or slurry reactor. In a further embodiment of the invention, the solution of the metal compound according to the invention is mixed with the solution of the activating agent, the resulting mixture is allowed to react for some time and subsequently injected into the above reactor. In a preferred embodiment, the reaction time of the catalyst of the present invention with the activating agent before the feed into the reactor is at least 1 second, preferably at least 5 minutes and even more preferably from 5 to 60 minutes. Said catalyst and activating agent are

31925 / T

Γ β r e

T t> r t r r C t r r r- t r r r <r. · R, · f.

yyyy * rp nr · - yyyy. rr r C C f 1 'Γ- _<T

r.-r-rr, rr * rn _n in the solution usually present at a concentration of from 0.0001 to 0.200 mol / liter, preferably from 0.001 to 0.05 mol / liter, more preferably from 0.005 to 0.025 mol / liter. Generally, the metal compound and the activating agent of the present invention are mixed together in a ratio of from about 1,000: 1 to about 0.5: 1. In a preferred embodiment of the present invention, the metal compound and the activating agent of the present invention are mixed together in a ratio of from about 300: 1 to about 1: 1, preferably from about 10: 1 to about 1: 1, in the case of borates, said ratio is preferably from about 1: 1 to about 10: 1 and in the case of aluminum compounds (such as diethylaluminum chloride in a mixture with water), said ratio is preferably from about 0.5: 1 to about 10: 1.

According to a further embodiment of the present invention, the catalyst system consists of a compound of a transition metal (catalyst) and / or an activating agent (cocatalyst), which are preferably injected into the reactor in the form of a solution. Solutions of said metal compounds are prepared by dissolving the catalyst in any solvent such as alkane, toluene, xylene, etc. Said solvent may be pre-purified to remove any catalytic poisons that could affect the activity of the catalyst, the group including traces of water and / or oxygen compound. Purification of the solvent may be achieved, for example, by using activated alumina and activated copper-based catalyst supported on a suitable support. The catalyst of the present invention is preferably completely dissolved to form a homogeneous solution. Both the catalyst and the activating agent can be dissolved in the same solvent if desired. After dissolution of the catalyst, the resulting solution can be stored until use.

From the viewpoint of polymerization, it is preferred that the catalyst of the present invention is mixed with the activating agent prior to injection into the reactor. Further, it is possible to add additional solvents to the catalyst solutions (directly on the production line or off-line), to the activating agent (directly on the production line or off-line), or to the activated catalyst (s).

31925 / T r r, r r r

C «3 o n

In a preferred embodiment, the productivity of the catalyst system of the present invention is 10,000 g of polymer per gram of catalyst per hour.

The catalyst system of the present invention injected in the solution described above has excellent functionality over a wide range of reactor conditions and can be used to produce polymers having a melt flow index of from 0.2 g / 10 min to 3 g / 10 min and the density ranges from 0.950 g / cm ³ to 0.916 g / cm ³ . When using the catalyst system of the present invention, no problems of agglomeration or layering of the resulting polymer were noticed during the 10 day continuous pilot scale operation. An advantage of the present invention is also the fact that there is no or little blockage of the reactor. No layers, lumps or large polymer particles were observed during or after the polymerization process. Likewise, no traces of polymer deposition were observed on the internal walls of the reactor or in the ducts used to circulate the gas. Likewise, there was no increase in pressure drop along the heat exchanger, in the circulating gas compressor or in the gas distribution plate throughout the process.

Injection of mixed catalyst system solutions

According to a further embodiment of the present invention, the mixed catalyst systems and / or the activating agent (cocatalyst) are injected into the reactor in the form of a solution. Solutions of said metal compounds are prepared by dissolving the catalyst in any solvent such as alkane, toluene, xylene, etc. Said solvent may be pre-purified to remove any catalytic poisons that could affect the activity of the catalyst, the group including traces of water and / or oxygen compound. Purification of the solvent may be achieved, for example, by using activated alumina and activated copper-based catalyst supported on a suitable support. The catalyst of the present invention is preferably completely dissolved to form a homogeneous solution. Both catalyst and activation

31925 / T e · β β e e e e r e r <

The reagent may be dissolved in the same solvent, if desired. After dissolution of the catalyst, the resulting solution can be stored until use.

From the viewpoint of polymerization, it is preferred that the catalyst of the present invention is mixed with the activating agent prior to injection into the reactor. Further, it is possible to add additional solvents to catalyst solutions (on-line or off-line), to an activating agent (on-line or off-line), or to activated catalyst (s), see U.S. Pat. Nos. 5,317,036 and U.S. Pat. No. 5,693,727 and European Patent Application Publication No. EP 0 593 083, the contents of which are incorporated herein by reference, and which disclose systems for injecting solutions into a reactor. There are many different configurations that can be used to mix catalysts and activating agents.

The catalyst systems, metal compounds and / or activating agent (s) of the present invention may be fed to the reactor in one or more solutions. Said metal compounds can be activated independently, either in series or together. In one embodiment, a solution of two activated metal compounds of the invention in an alkane such as pentane, hexane, toluene, isopentane and the like is injected into a gas phase or slurry polymerization reactor. In another embodiment, the catalyst system or components of the invention may be injected into the reactor in the form of a suspension or emulsion. In another embodiment, the second metal compound of the invention is contacted with the above-described activating agent, such as modified methylalumoxane, in solution and just prior to spraying the solution into the gas phase, slurry, or solution polymerization reactor. A solution of a metal compound containing a Group 15 element is mixed with a solution of said second compound and an activator and subsequently injected into the reactor.

In the schemes described below, stream A is a catalyst or catalyst mixture, and stream B is another catalyst or catalyst mixture. The catalyst mixtures in streams A and B may consist of the same catalysts, which are mixed in different proportions. Next is

It should be noted that in many places additional solvents or inert gases may be added to streams A and B.

Scheme 1: Streams A and B together with the activating agent are mixed together outside the production line and the resulting mixture is subsequently injected into the reactor. This diagram is shown in the attached Figure 1.

Scheme 2: Streams A and B are mixed together outside the production line. An activating agent is added to the resulting mixture directly on the production line and the resulting mixture is injected into the reactor. This diagram is shown in the attached Figure 2.

Scheme 3: Stream A or B is contacted (including the production line) with an activating agent, and stream A or B is added directly to the resulting mixture directly on the production line prior to entering the reactor. This scheme is shown in Figure 3.

Scheme 4: Stream A or B is contacted (directly on the production line) with the activating agent, and stream A or B is added to the resulting mixture directly on the production line prior to entering the reactor. This scheme is shown in Figure 4.

Scheme 5: Both streams A and B are contacted off-line with the activating agent. Subsequently, stream A containing the activating agent is contacted directly on the production line prior to entering the reactor with stream B containing the activating agent. This diagram is shown in the attached Figure 5.

Scheme 6: Both streams A and B are contacted directly with the activating agent directly on the production line. Subsequently, stream A containing the activating agent is contacted directly on the production line prior to entering the reactor with stream B containing the activating agent. (This arrangement is advantageous because the ratio of stream A to stream B and the ratio of activating agent to stream A and the ratio of activating agent to stream B can be independently controlled). This diagram is shown in the attached Figure 6.

31925 / T • r>

·. r r r r · · · · · · 'r f' - r 'r

Scheme 7: In this case, stream A or B is contacted (directly on the production line) with the activating agent, while separate solution A or B is contacted with the activating agent outside the production line. Subsequently, both streams A or B and the activating agent are contacted directly on the production line before entering the reactor. This diagram is shown in the attached Figure 7.

Scheme 8: Stream A is directly contacted with stream B directly on the production line. Subsequently, an activating agent is fed directly to the mixture of A and B directly on the production line. This scheme is shown in the attached Figure 8.

Scheme 9: Stream A is activated off-line using an activating agent. Thereafter, stream A containing the activating agent is contacted directly on the production line with stream B. To the resulting mixture of stream A, B and activating agent, a further proportion of activating agent is added directly on the production line. This diagram is shown in the attached Figure 9.

In all the arrangements described above, means may be used to ensure complete mixing of the individual components and / or to provide a certain residence time. For example, mixing blades or worms may be used to mix said components, or pipelines of a certain length may be used to achieve the desired contact time of each component or residence time. By "directly on the production line" it is understood that the described material is present in a pipeline, tube or vessel that is directly or indirectly connected to the reactor system. By &quot; off-line &quot; it is meant that the described material is present in a pipe, tube or vessel that is not connected to the reactor system.

In another embodiment, the invention relates to a process for the polymerization of olefins in a gas-phase polymerization reactor in which at least two catalysts and at least one activating agent are injected, the catalysts and the activating agent being injected using a liquid carrier. In a preferred embodiment said catalysts and activating agent (s) are mixed together in a liquid carrier prior to injection into the reactor.

31925 / Tt 1

In another embodiment of the present invention, the catalysts are mixed together in a liquid carrier, then fed to a distribution device connected to the reactor, and then the activating agent (s) is fed to the distribution device, wherein the activating agent (s) is they can be introduced into said composition both at the same site as the catalysts and at a completely different site. In a further embodiment of the invention, said catalysts are contacted together in a liquid carrier and then one or more activating agents are added to the liquid carrier.

According to another embodiment of the present invention, a liquid carrier comprising said catalysts and an activating agent (s) is fed to a liquid carrier injection apparatus into the above polymerization reactor. In another variation, said catalysts and the liquid carrier are fed to the device before the activating agent is fed to the device.

In another preferred embodiment of the present invention, said composition comprising a liquid carrier forms a liquid stream that flows or is sprayed into the reactor.

In a further preferred embodiment of the present invention, at least one catalyst, at least one activating agent and a liquid carrier are fed to the reactor injection apparatus, and after the first catalyst and activating agent is fed to the apparatus, another (i.e. ) catalyst (s).

The polymerization process of the invention,

The catalyst compositions, catalyst systems, mixed catalyst systems, supported catalyst systems or solution sprayed catalyst systems of the present invention described above are suitable for use in any polymerization process. The polymerization process of the present invention comprises solution, gas phase or suspension polymerization

31925 / T 4 4 * * f f f

C r. *. «J .c f t r. · R f

Γ f f ·. r Z r - r <-,

Γ r r. The combination of these processes, but most preferably gas phase or slurry polymerization, and even more preferably, the polymerization process of the present invention comprises the use of a single reactor, most preferably a single gas phase polymerization reactor.

One aspect of the present invention is a slurry or gas phase polymerization or copolymerization reaction comprising the polymerization of one or more monomers having from 2 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and more preferably from 2 to 8 carbon atoms. The process of the present invention is particularly suitable for copolymerization reactions involving the polymerization of one or more olefin monomers selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene , 3-methyl-1-pentene, 3,3,5-trimethyl-1-hexene and cyclic olefins or mixtures thereof. Other monomers may include vinyl monomers, diolefins such as dienes, polyene monomers, norbornene monomers, norbornadiene monomers. Preferably, according to the present invention, a copolymer of ethylene and at least one comonomer selected from the group consisting of alpha-olefins containing from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, more preferably from 4 to 8 carbon atoms and most preferably from 4 to 7 carbon atoms is produced. . In another embodiment of the present invention, it is possible to polymerize or copolymerize the geminally disubstituted olefins described in WO 98/37109.

According to another embodiment of the present invention, ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer. A group of preferred comonomers according to the invention comprises a mixture of alpha-olefin monomers having from 4 to 10 carbon atoms, more preferably from 4 to 8 carbon atoms, optionally with at least one diene monomer. Preferred terpolymers of the present invention include mixtures such as ethylene / 1-butene / 1-hexene, ethylene / propylene / 1-butene, propylene / ethylene / 1-hexene, ethylene / propylene / norbornene, and the like.

31925 / T

A particularly preferred embodiment of the present invention relates to the polymerization of ethylene and at least one comonomer containing from 3 to 8 carbon atoms, preferably from 4 to 7 carbon atoms. Examples of such comonomers are 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene, with 1-hexene and / or 1-butene being the most preferred comonomers.

The gas phase polymerization of the present invention typically utilizes a continuous cycle in which one part of the cycle, consisting of a reactor system circulating a gas stream, referred to as a recycle stream or fluid, is heated in said reactor by the heat released by the reactor. polymerization. This heat is removed from the recycle mixture in another part of the circuit by means of a cooling system located outside the reactor. In the process for producing a fluidized bed gas phase polymer, a gas stream containing one or more monomers is typically circulated through the fluidized bed continuously in the presence of a catalyst and under conditions where the desired reaction takes place. Said gas stream is discharged from said fluidized bed and recycled back to the reactor. In parallel to this process, the polymerization product is removed from the reactor and the fresh monomer is injected to replace the polymerized monomer. (See, for example, U.S. Patent Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661, and 5,668,228, which are incorporated herein by reference. .

The pressure in the gas-phase polymerization reactor may vary from about 69 kilopascals. (about 10 psig) to about 3,448 kilopascals (about 500 psig), preferably in the range of about 690 kilopascals (about 100 psig) to about 2,759 kilopascals (about 400 psig), preferably in the range of about 1379 kilopascals (about 200 psig) ) to about 2759 kilopascals (about 400 psig), more preferably in the range of about 1,724 kilopascals (about 250 psig) to about 2,414 kilopascals (about 350 psig).

31925 / T r

The temperature in the gas-phase polymerization reactor may vary from about 30 ° C to about 120 ° C, preferably from about 60 ° C to about 115 ° C, more preferably from about 75 ° C to about 110 ° C. And most preferably in the range of about 85 ° C to about 110 ° C. Temperature changes in the polymerization can be used as a tool to change the properties of the resulting polymerization product.

The productivity of the catalyst or catalyst system of the present invention is affected by the partial pressure of the main monomer. Preferably, the molar percentage content of the main monomer of the present invention, i.e. ethylene or propylene, preferably ethylene, is from about 25 mole% to 90 mole%, the partial pressure of said monomer being in the range of about 517 kilopascals (about 75 psig) up to about 2,069 kilopascals (about 300 psig), which are common conditions for a gas phase polymerization process. In one embodiment of the present invention, the ethylene partial pressure is from about 1,517 kilopascals to about 1,653 kilopascals (from about 220 psig to 240 psig). In another embodiment of the invention, the molar ratio of hexene to ethylene in the reactor is from 0.03: 1 to 0.08: 1.

In a further embodiment of the present invention, it is possible to produce from more than 227 kg of polymer / hour (ie, more than 500 Ib of polymer / hour) to about 90 900 kg or more of polymer by the reactor used in the present invention and the process of the present invention. an hour (ie, about 200,000 Ib or more of polymer / hour), preferably from more than 455 kg of polymer / hour (ie, more than 1,000 Ib of polymer / hour), more preferably from more than 4,540 kg of polymer / hour (ie, more than 10 More preferably from more than 11,300 kg of polymer / hour (i.e. more than 25,000 Ib of polymer / hour), even more preferably from more than 15,900 kg of polymer / hour (i.e. more than 35,000 Ib of polymer / hour) more preferably from more than 22,700 kg polymer / hour (ie more than 50,000 Ib polymer / hour) and more preferably from more than 29,000 kg polymer / hour (ie more than 65,000 Ib polymer / hour) to more than 45,500 kg polymer / hour (i.e., greater than 100,000 Ib polymer / hour).

31925 / T er rcr <* <* ^r trcricr C r <, rrrfrrrr, r. . -zrcrrrrrcr> · tefrppr 1

Other gas phase polymerization processes considered to be methods of the present invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375, European Patent Applications EP-A-0 794 200, EP- A-0 802 202 and EP-B-634 421, the contents of all of which are incorporated herein by reference.

Suspension polymerization typically uses a pressure in the range of from about 103 kilopascals to about 5,068 kilopascals (i.e., from about 1 atmosphere to about 50 atmospheres) and even more, with a temperature ranging from 0 ° C to about 120 ° C. Suspension polymerization results in a suspension of a solid, particulate polymer in a liquid polymerization medium containing a solvent to which ethylene is added along with the comonomers and the catalyst. Said solvent-containing slurry is intermittently or continuously removed from the reactor, where the volatile components are separated from the polymer, which are recycled, optionally after distillation, back to the reactor. The liquid solvent to be used in said polymerization medium is usually an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium used should be liquid and relatively inert under polymerization conditions. If a propane medium is used, said process must be carried out at a pressure and temperature above the critical temperature and critical pressure of said reaction solvent. Preferably, a hexane or isobutane medium is used according to the invention.

In one embodiment, the preferred polymerization process of the present invention is polymerization in which solid polymer particles or slurry polymerization are maintained at a temperature lower than that in which the polymer would dissolve. Such procedures are well known in the art and have been described, for example, in U.S. Patent No. 5,901,849. No. 3,248,179, which is incorporated herein by reference. In the method of forming solid polymer particles, the temperature is preferably maintained in the range of about 85 ° C

31925 / T e e c r λ i c -. r

C e r ft <· yy yy yy yy yy yy yy yy yyyy yyyy yyyyy,

Ir Γ Γ <7 · _a · (| '·' · (about 185 ° F) to about 110 ° C (about 230 ° F). In a slurry polymerization, preferred two methods, wherein the one method, the using a loop reactor, while the latter uses several stirred reactors connected in series, in parallel, or a combination of the above mentioned connections of the individual reactors, as an example of a slurry polymerization process and a continuous loop process without a stirred reactor. Other examples of slurry polymerization methods have also been described in U.S. Patent No. 4,613,484, which is incorporated herein by reference.

In another embodiment of the present invention, the slurry polymerization is carried out continuously in a loop reactor. The catalyst in the form of a suspension in isobutane or in the form of a dry, free-flowing powder is regularly fed to a reactor loop which itself is filled with a circulating suspension of increasing polymerization particles in a solvent which is an isobutane-containing monomer and comonomer. Optionally, hydrogen may be introduced into the system to control the molecular weight of the polymer formed. The reactor pressure is maintained at about 3,620 kilopascals (about 525 psig) to about 4,330 kilopascals (625 ₎ psig), and the temperature in the reactor is from about 60 ° C (about 140 ° F) to about 104 ° C (approximately 220 ° F), depending on the desired density of the polymer formed. Reaction heat is dissipated through the loop wall because most of this reactor is in the form of a double-jacketed pipeline. The slurry is allowed to leave the reactor at regular intervals or continuously to a heated low pressure firing vessel, a rotary dryer and a nitrogen purge column to remove the isobutane solvent and any unreacted monomer and comonomers. The resulting hydrocarbon-free powder is subsequently used in various products.

In an embodiment of the present invention, the reactor used in the slurry polymerization of the present invention can be

31925 / T according to the method of the present invention to produce more than 907 kg polymer / hour (ie more than 2000 lb polymer / hour), more preferably more than 2 268 kg polymer / hour (ie more than 5,000 lb polymer / hour) and most preferably more greater than 4,540 kg polymer / hour (i.e., greater than 10,000 lbs polymer / hour). In another embodiment of the present invention, it is possible to produce from a slurry polymerization reactor of more than 6,804 kg of polymer / hour (i.e. more than 15,000 lb of polymer / hour), preferably from more than 11,340 kg polymer per hour (ie, greater than 25,000 lb polymer / hour) to about 45,500 kg polymer / hour (ie, greater than 100,000 lb polymer / hour).

In another embodiment of the slurry polymerization process of the present invention, the total reactor pressure is in the range of 2758 kilopascals (ie 400 psig) to 5,516 kilopascals (ie 800 psig), preferably in the range of 3,103 kilopascals (ie 450 psig) to about 4 827 kilopascals (ie, about 700 psig), more preferably in the range of 3,448 kilopascals (ie, 500 psig) to about 4,482 kilopascals (ie, about 650 psig), and most preferably in the range of about 3,620 kilopascals (ie, about 525 psig) to 4,330 kilopascals (i.e., about 625 psig).

In another embodiment of the slurry polymerization of the present invention, the concentration of ethylene in said reactor fluid medium is in the range of about 1 wt. % to 10 wt. %, preferably in the range of about 2 wt. % to about 7 wt. %, more preferably in the range of about 2.5 wt. % to about 6 wt. %, most preferably in the range of about 3 wt. % to about 6 wt. %.

I

Another method of the present invention is a process, preferably gas phase or suspension polymerization, which is carried out in the absence or substantially free of any scavengers such as triethyl aluminum, trimethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum and diethylaluminum chloride, dibutyl zinc . Such a method has been described in International Publication No. WO 96/08520 and in U.S. Pat.

31925 / T r. r r c r r r r r r f. No. 1, incorporated by reference into U.S. Pat. No. 5,712,352, the contents of which are incorporated herein by reference.

In a preferred embodiment of the present invention, a suspension of aluminum stearate in mineral oil is sprayed either separately or together with the first and / or second metal complexes of the invention and / or together with the activating agent described above. For a more detailed discussion of the use of aluminum stearate type additives, see U.S. Patent Application Ser. No. 09 / 113,261 of July 10, 1998, the contents of which are incorporated herein by reference.

In an embodiment of the present invention wherein the second metal compound of the present invention and the metal compound comprising a Group 15 element are added to the reactor sequentially, it is preferred that said second metal compound is added and / or activated first and said compound The metal containing the Group 15 element of the Periodic Table of Elements is added to the reactor and / or activated second.

In another embodiment, the residence time of the catalyst composition of the invention is from about 3 hours to about 6 hours, preferably from about 3.5 hours to about 5 hours.

T

The molar ratio of comonomer to ethylene of the present invention, referred to as C _x / C 2, wherein C _x is the amount of comonomer and C 2 is the amount of ethylene, is in the range of about 0.001 to 0.0100 and more preferably about 0.002 to 0.008.

The melt index (and other properties) of the polymer produced according to the present invention can be varied by adjusting the hydrogen concentration in the polymerization system by:

1. varying the amount of the first catalyst in the polymerization system; and / or

2. varying the amount of second catalyst in the polymerization system; and / or

3. adding hydrogen to the polymerization process; and / or

31925 / T

Γ Γ.

c n ť r. r r c ,, r r r r r t- t c r r »cr r c r r. r c r r r r r r c

4. changes in the amount of liquid and / or gas that is discharged and / or discharged from the reactor and / or

5. changes in the amount and / or composition of the recovered liquid and / or recovered gas that are returned to the polymerization process, wherein said liquid or said gas is recovered from the polymer taken from the polymerization process, and / or

6. use of a hydrogenation catalyst in the polymerization process and / or

7. temperature changes during polymerization; and / or

8. changes in ethylene partial pressure in the polymerization process; and / or

9. changes in the ethylene to hexene ratio in the polymerization process; and / or

10. changing the ratio of activating agent to transition metal in the activating sequence.

The hydrogen concentration in the above reactor is from about 100 ppm to 5,000 ppm, preferably from 200 ppm to 2,000 ppm, more preferably from 250 ppm to 1,900 ppm, more preferably from 300 ppm to 1,800 ppm, more preferably from 350 ppm to 1,700 ppm, more preferably from 400 ppm to 1600 ppm, more preferably from 500 ppm to 1500 ppm, more preferably from 500 ppm to 1400 ppm, more preferably from 500 ppm to 1200 ppm, more preferably from 600 ppm to 1200 ppm, more preferably from 700 ppm to 1100 ppm and even more preferably from 800 ppm to 1000 ppm. The hydrogen concentration in the reactor is inversely proportional to the weight average molecular weight (M _w ) of the resulting polymer.

Polymer according to the present invention

Polymers produced by the methods of the present invention can be used in many different products and end applications. The group of polymers produced by the methods of the present invention includes polyethylene and bimodal polyethylene produced in a single reactor using the mixed catalyst system of the present invention. In addition to bimodal polymers, they belong to the group of polymers made using blend

31925 / T tCC rrrrrrrrrrrrrrr. r t r r ø 9 ø. mono- or multimodal polymers.

The use of the compound itself containing metal Group 15 elements produce polymers with high weight average molecular weight (M _{w) of,} for example polymers of molecular weight greater than 100,000, preferably greater than 150 000, preferably of more than 200 000 Preferably, the second metal compound of the present invention produces polymers having a low weight average molecular weight, such as polymers having a molecular weight of less than 80,000, preferably less than 70,000, preferably less than 70,000, preferably less than 70,000, preferably less than 70,000. less than 60,000, preferably less than 50,000, preferably less than 40,000, preferably less than 30,000, preferably less than 20,000, and greater than 5,000, more preferably less than 20,000, but greater than 10,000.

The polyolefins, especially the polyethylenes produced by the process of the present invention, have a density ranging from 0.88 g / cm ³ to 0.97 g / cm ³ (measured in accordance with ASTM 2839). Preferably, it is possible to produce polyethylenes having a density in the range of 0.910 g / cm ³ to 0.965 g / cm ³ , more preferably in the range of 0.915 g / cm ³ to 0.960 g / cm ³ , more preferably in the range of 0.920 g / cm ³ to 0.955 g / cm ³ . In some cases it may be advantageous to produce a polymer with a density in the range of 0.915 g / cm ³ to 0.940 g / cm ³ , in other cases it may be advantageous to produce a polymer with a density in the range of 0.930 g / cm ³ to 0.970 g / cm ³ .

In a preferred embodiment, the melt index ₁₂ (measured according to ASTM D-1238, condition E, 190 ° C) of the polyolefin produced according to the present invention ranges from about 0.01 g / 10 minutes to about 1000 g / 10 minutes . Preferably, the polyolefin is an ethylene homopolymer or copolymer. In a preferred embodiment of the present invention, when the produced polymer is used to produce certain articles such as films, tubes, shaped articles and the like, it is preferred that the melt index of the polymer be 10 g / 10 minutes or less. For the production of some types of foils and molded

31925 / T e e e e e e * r f yy r

C r r r

C ^L C L ~ cl RRTRR rrr I '<'

Γ r / r p p r. c '

Γ products are preferred if the melt index is 1 g / 10 minutes or less. A preferred polymer is polyethylene having a melt index ranging from 0.01 g / 10 minutes to 10 g / 10 minutes.

In a preferred embodiment, the melt index I21 (measured according to ASTM D-1238 standard, condition F, 190 ° C) of the polymer produced according to the invention is in the range of 0.1 g / 10 min to 10 g / 10 min preferably y is from 0.2 g / 10 minutes to 7.5 g / 10 minutes, more preferably the index is 2 g / 10 minutes or less, preferably 1.5 g / 10 minutes or less, preferably 1.2 g 10 min or less, more preferably 0.5 g / 10 min to 1.0 g / 10 min, even more preferably 0.6 g / 10 min to 0.8 g / 10 min.

In another embodiment of the invention, the index ratio MFI (MIR) l ₂₁ / l ₂ 80 or more, preferably 90 or more, preferably 100, preferably 125 or more.

According to another embodiment of the present invention, the melt index of ₁₂ i (measured according to ASTM D-1238, condition F, 190 ° C) of the polymer produced according to the invention is 2 g / 10 minutes or less, preferably

1.5 g / 10 minutes or less, preferably 1.2 g / 10 minutes or less, more preferably in the range 0.5 g / 10 minutes to 1.0 g / 10 minutes, even more preferably in the range 0.6 g / 10 minutes (10 minutes to 0.8 g / 10 minutes) and the melt index ratio I21 / I2 is 80 or more, preferably 90 or more, preferably 100, preferably 125 or more, and in addition the polymer has the following characteristics:

a) a molecular weight distribution (M _w / M _n ) ranging from 15 to 80, preferably from 20 to 60, preferably from 20 to 40, wherein the individual molecular weights M _w and M _n are measured as described in the Examples;

b) the weight average molecular weight (M _w) of 180,000 or more, preferably 200,000 or more, more preferably 250,000 or more, even more preferably 300,000 or more,

31925 / T ceer · f * prefefecp for crcrcrrc OO ^r

c) a density (determined in accordance with ASTM 2839) in the range of 0.94 g / cm ³ to 0.970 g / cm ³ , preferably in the range of 0.945 g / cm ³ to 0.965 g / cm ³ , preferably in the range of 0.950 g / cm ³ to 0.960 g / cm ³ ,

d) a residual transition metal content of 5.0 ppm or less, preferably 2.0 ppm or less, preferably 1.8 ppm or less, preferably 1.6 ppm or less, preferably 1.5 ppm or less, preferably 2.0 ppm or less metal of 4.

a group of the Periodic Table of the Elements, preferably 1.8 ppm or less of the metal of 4.

a group of the Periodic Table of the Elements, preferably 1.6 ppm or less of the metal of 4.

a group of the Periodic Table of the Elements, preferably 1.5 ppm or less of the metal of 4.

groups of the Periodic Table of the Elements, preferably 2.0 ppm or less zirconium, preferably 1.8 ppm or less zirconium, preferably 1.6 ppm or less zirconium, preferably 1.5 ppm or less zirconium (measured by inductively coupled plasma optical emission spectroscopy ( ICPAES)), the measurement being carried out against commercially available standards, where the individual samples are heated to complete decomposition of all organic matter, the solvent used comprises nitric acid and, if any carrier material is present, said solvent contains an additional acid , which serves to dissolve the carrier (such as hydrofluoric acid to dissolve the silica),

e) it contains 35 wt. % or more of the high molecular weight component, as determined by particle size chromatography, preferably comprises 40 wt. % or more of said component. In a particularly preferred embodiment, the higher molecular weight component in the polymer of the present invention is present in an amount of from 35 to 70 wt. %, more preferably in an amount of from 40 to 60 wt. %.

In a preferred embodiment, the catalyst system described above is used to produce polyethylene having a density between 0.94 g / cm ³ and 0.970 g / cm ³ (measured according to ASTM D-2839), whose melt index ₁₂ is 0.5 g / cm 2. 10 minutes or less.

In another embodiment, the catalyst described above is used to make polyethylene, the melt flow rate ₂₁ l is less than 10 g / 10

31925 / T c r r r c

ft errer ^f r> crcr ^r * rcrrf · r r. cfc <^'y y C · rrr min and a density between about 0.940 g / cm ³ to 0.950 g / cm ³ and the melt index, I21 less than 20 g / 10 min and a density of about 0.945 g / cm ³ or less.

In another embodiment, the polymer of the present invention is used for the manufacture of tubes by known methods. In this case, the polymer used to manufacture the tubes has a melt index I21 of from about 2 g / 10 minutes to about 10 g / 10 minutes, preferably from about 2 g / 10 minutes to about 8 g / 10 minutes. According to another embodiment, the tubes of the present invention meet the quality requirements of the ISO standard.

In another embodiment of the present invention, the catalyst of the present invention is used to produce polyethylene tubes having a service life of at least 50 years at 20 ° C, using water as the internal test medium and water or air as the external environment (Hydrostatic (contact)) voltage measured according to ISO TR 9080).

In another embodiment of the present invention, the resulting polymer has a scratch resistance test of notched pipes (a slow crack propagation test) of more than 150 hours at 3.0 megapascals, preferably more than 500 hours at 3.0 megapascals, and still more. more preferably, more than 600 hours at a pressure of 3.0 megapascals (measured in accordance with ASTM-F1473).

In another embodiment of the present invention, the catalyst composition of the present invention is used to produce polyethylene pipes having a predicted S-4 T _{c value} for a pipe length of 110 mm less than -5 ° C, preferably less than -15 ° C, and more preferably less as -40 ° C (measured according to ISO DIS 13477 / ASTM F1589).

According to another embodiment of the present invention, the produced polymer can be extruded at a rate of greater than about 3 kg / hr / cm slot circumference (ie, greater than about 17 pounds / hour / inch slot circumference), preferably above about 3.5 kg / hr. cm of slot circumference (i.e., greater than about 20 pounds / hour / inch of circumference) and more preferably greater than about 3.9

31925 / T kg / hr / cm slot circumference (i.e., greater than about 22 pounds / hour / inch slot circumference).

The polyolefins of the present invention can be processed into films, shaped articles (including tubes), plates, wire and cable coating materials and the like. Said films may be produced by conventional methods known in the art, the group of which comprises extrusion, co-extrusion, lamination, blow molding and casting. The film may be obtained in the form of a flat film or by a process to produce a film in the form of a sleeve, followed by orientation of the film in one or two directions perpendicular to one another in the plane of the film, to the same or different extent. The extent of said orientation may be the same in both directions or may be different in each direction. A group of particularly preferred processes for processing the polymers of the present invention to form films include extrusion or co-extrusion on a blown or flat film production apparatus.

In a further embodiment of the present invention, the produced polymer is processed to a film shape by known methods. In this case, the melt index of both the ₁₂ and the polymers of the present invention is in the range of about 2 g / 10 minutes to about 50 g / 10 minutes, preferably in the range of about 2 g / 10 minutes to about 30 g / 10 minutes, more preferably in the range of about 5 g / 10 minutes to about 15 g / 10 minutes, and even more preferably in the range of about 5 g / 10 minutes to about 10 g / 10 minutes.

According to another embodiment of the present invention, the tear resistance of the film having a thickness of 13 µm (0.5 mil) in the machine direction (MD) is in the range of about 5 g / mil to 25 g / mil, preferably in the range of about 15 g / mil to 25 g / ml and more preferably in the range of about 20 g / ml to 25 g / ml.

The films made according to the invention may further comprise additives such as glidants, anti-blocking agents, antioxidants, pigments, fillers, anti-turbidity agents, anti-ultraviolet stabilizing agents, antistatic agents, polymer processing agents, neutralizing agents, lubricants, surfactants,

31925 / T e · _{e e e e e} err err err err err err err err err ivá far far far ivá Preferred additives include silica, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metal atom stearates, calcium stearate, zinc stearate, clay, barium sulfate, diatomaceous earth, wax, carbon black, flame retardants, low molecular weight polymers, glass beads and the like. Said additives are usually used in an amount which is sufficient for their effective action, these amounts being well known in the art and can be, for example, from 0.001 wt. % to 10 wt. %.

In another embodiment of the present invention, the produced polymer is processed by conventional methods into a shaped article, for example by blow molding and injection molding. The polymers of the present invention which are used in the manufacture of shaped articles have a melt index of ₁₂ iv in the range of about 20 g / 10 minutes to about 50 g / 10 minutes and preferably in the range of about 35 g / 10 minutes to about 45 g / 10 minutes.

According to another embodiment of the present invention, the polymers of the present invention, including the polymers described above, contain less than 100 ppm ash, more preferably less than 75 ppm and even more preferably less than 50 ppm. In another embodiment, said ash contains a negligible low amount of titanium, the amount of which is determined by a combination of inductively coupled plasma emission spectroscopy and atomic emission spectroscopy (ICPAES), a method well known in the field of analytical chemistry.

In another embodiment of the invention, the polymers produced contain a nitrogen-containing ligand that can be detected by high resolution mass spectroscopy (HRMS), which is again a well-known analytical method.

31925 / T three

r. r f r r ** * c

BRIEF DESCRIPTION OF THE DRAWINGS

Figures 1 to 9 show the above-described schemes for the possible arrangement of injection of the individual catalyst components of the present invention into a polymerization reactor.

DETAILED DESCRIPTION OF THE INVENTION

For a better understanding of the nature of the invention, including its selected advantages, the following examples are provided without limiting the scope thereof.

The weight average molecular weight (M _w ) and number average molecular weight (M _n ) were measured by gel permeation chromatography on a Waters 150 ° C GPC equipped with differential detectors operating on the basis of refractive index measurements. Gel permeation chromatography (GPC) columns were calibrated using a series of narrow polystyrene standards with a narrow molecular weight range and the given molecular weights were calculated using Mark Houwink coefficients for the respective polymer.

The molecular weight distribution (MWD) is the ratio M _w / M _n .

The density was measured in accordance with ASTM D 1505.

The mixture distribution index (CDBI) was measured according to the procedure described in published international application number WO, 93/03093, except for fractions whose number average molecular weight was less than 10,000 which were neglected in the calculation.

The melt flow index (M1) ₁₂ was measured in accordance with ASTM standard 1238, condition E, at 190 ° C. The melt flow index (M1) I21 was measured according to ASTM standard 1238, condition F, at 190 ° C.

Melt Index Ratio (MIR) is the ratio of the melt index of ₂₁ l and a melt index l ₂ to be measured according to ASTM 1238th

31925 / T

C rr · * C

The comonomer content, expressed as a percentage by weight, was measured by proton NMR spectroscopy.

The impact strength tested by falling arrow was determined in accordance with ASTM D 1709.

Elmendorf tear resistance in the machine direction (MD) and in the transverse direction (TD) was measured according to ASTM D 1922.

% secant, i. the modulus of elasticity, determined as tangent to the stress strain curve, was determined in accordance with ASTM D 822.

The tensile strength and ultimate tensile strength in the machine direction (MD) and in the transverse direction (TD) were measured in accordance with ASTM D 822.

Ductility and ultimate ductility in machine direction (MD) and transverse direction (TD) were measured in accordance with ASTM standard 822-91.

Turbidity was measured according to ASTM standard 1003-95, condition A.

The gloss at 45 ° was measured according to ASTM D 2457.

BUR stands for blowing ratio.

The 26-inch falling arrow impact strength was determined in accordance with ASTM D 1709, Method A.

Escorene® LL3002.32 is a linear low density ethylene-hexene copolymer made in a single gas-phase polymerization reactor using a Ziegler-Natta catalyst commercially available from Exxon Chemical Company, Houston, Texas, USA. The density of this polymer is 0.918 g / cm ³ , its melt index ₁₂ is 2 g / 10 minutes and the branch distribution index (CDBI) of the polymer is less than 65.

Exceed® ECD 125 is a linear low density ethylene-hexene copolymer made in a single gas phase polymerization reactor and using a metallocene catalyst, which is commercially available from Exxon Chemical Company, Houston, Texas, USA. The density of this polymer is 0.91 g / cm ³ and its melt index is 1.5 g / 10 minutes.

31925 / T e'e e · e c

Escorene® LL3001.63 is a linear low density ethylene-hexene copolymer made in a single gas-phase polymerization reactor using a Ziegler-Natta catalyst, commercially available from Exxon Chemical Company, Houston, Texas, USA. The density of this polymer is 0.918 g / cm ³ , its melt index ₁₂ is 1.0 g / 10 minutes.

Exceed® 350D60 is a linear low density ethylene-hexene copolymer made in a single gas-phase polymerization reactor using a metallocene catalyst commercially available from Exxon Chemical Company, Houston, Texas, USA. The density of this polymer is 0.918 g / cm ³ and its melt index is 1.0 g / 10 minutes.

PPH stands for pounds / hour, mPPH stands for millilibres / hour. The abbreviation "pprnw" refers to units of ppm expressed in parts by weight.

In the examples described in Example I, a mixed catalyst system was used comprising a metal catalyst comprising a Group 15 element of the Periodic Table of the Elements and a sterically bulky ligand metallocene catalyst.

Example Section I. A mixed catalyst system comprising a metal catalyst comprising a Group 15 element of the Periodic Table of the Elements and a sterically bulky ligand metallocene catalyst

Preparation of indenyl zirconium trispivate

Indenyl zirconium trispivalate, a sterically bulky metallocene compound represented by the formula (VI), could be prepared by the following chemical reactions:

(1) Zr (NEt ₂ ) ₄ + IndH indZr (NEt ₂ ) ₃ + Et ₂ NH (2) indZr (NEt ₂ ) ₃ + 3 (CH ₃ ) ₃ CCO ₂ H -> indZr [O ₂ CC (CH ₃₎ )] ₃ + Et ₂ NH where Ind is indenyl and Et is ethyl.

Preparation of ((2,4,6-Me ₃ C ₆ H ₂ ) NHCH ₂ CH ₂ ) ₂ NH (ligand I)

31925 / T

In a 2 L Schlenk flask was placed a magnetic stirrer, 23.450 g (0.227 mole) of diethylenetriamine, 90.51 g (0.455 mole) of 2-bromo-mesitylene, 1.041 g (1.14 millimole) of tris (dibenzylideneacetone) dipalladium, 2.123. g (3.41 millimoles) of racemic 2,2'-bis (diphenylphosphino) -1,1-binaphthyl (racemic BINAP), 65.535 g (0.682 mol) of sodium tert-butoxide and 800 ml of toluene. The reaction mixture was heated to 100 ° C with stirring. After stirring for 18 hours, the reaction was found to be complete by proton NMR spectroscopy. All remaining operations were already performed in the presence of air. The solvent was removed in vacuo and the residue dissolved in 1 L of ether. The ether solution was washed three times with 250 ml of water and 500 ml of saturated aqueous sodium chloride solution (in which 180 g of NaCl was dissolved) and dried over 30 g of anhydrous magnesium sulfate. Removal of the ether in vacuo yielded a red oil which was dried under vacuum at 70 ° C for 12 hours to give 71.10 g (92%) of the product.

¹ H NMR (C ₆ D ₆ ) δ 6.83 (s, 4), 3.39 (brs, 2), 2.86 (t, 4), 2.49 (t, 4), 2.27 ( s, 12), 2.21 (s, 6), 0.68 (brs, 1).

Preparation of Catalyst A (for the purpose of Example I)

A 1.5% catalyst solution in toluene was prepared by the following step sequence, all operations being carried out in a dry cabinet.

A 100 L purified toluene was weighed into a 1 L Erlenmeyer flask equipped with a Teflon coated stirrer. 7.28 g of tetrabenzyl zirconium were added to the toluene and the resulting solution was allowed to stir for 5 minutes, during which time all the solid dissolved. To the solution were added 5.42 g of ligand I as described above and an additional 551 g of purified toluene. The mixture was allowed to stir for 15 minutes, whereupon all solid dissolved again. The resulting catalyst solution was transferred to a clean 1 liter Whitey cylinder, which was subsequently labeled, removed from the dry cabinet, and placed in a holder for preparation for later use.

31925 / T

Alternative Preparation of Compound I {[(2A6-Me ₃ C ₆ H 2) NCH ₂ CH ₂ ] 2 NH} Zr (CH ₂ Ph) ₂

A magnetic stirrer was placed in a 500-ml round-bottom flask and 41.729 g (91.56 millimoles) of tetrabenzyl zirconium (Boulder Scientific) and 300 ml of toluene were added to the flask in a dry, nitrogen-free atmosphere. 32.773 g (96.52 millimoles) of solid ligand I, described above, were added to the mixture with stirring over a period of 1 minute to precipitate the desired product from the mixture. The volume of the suspension was reduced to 100 ml and 300 ml of pentane was added with stirring. The yellow-orange solid was collected by filtration and dried in vacuo to give 44.811 g (80%) of the desired product.

¹ H NMR (C ₆ D ₆ ) δ 7.22-6.81 (m, 12), 5.90 (d, 2), 3.38 (m, 2), 3.11 (m, 2), 3.01 (m, 1), 2.49 (m, 4), 2.43 (s, 6), 2.21 (s, 6), 2.18 (s, 6), 1.89 (s) , 2), 0.96 (s, 2) ·

Preparation of Catalyst B (for this Example I) A% catalyst solution in hexane was prepared by the following step-by-step procedure, all operations being carried out in a dry cabinet.

To a 1 L Erlenmeyer flask equipped with a Teflon-coated stirrer was charged 1 L of purified hexane. To the hexane was added 6.67 g of indenyl zirconium trispivalate as a dry powder. The resulting solution was allowed to stir for 15 minutes, during which time all solids dissolved. The resulting catalyst solution was transferred to a clean 1 liter Whitey cylinder, which was subsequently labeled, removed from the dry cabinet, and placed in a holder for preparation for later use.

Example Section I - Comparative Example 1

In a 35.6 cm (14 inch) gas phase polymerization pilot plant operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water-cooled exchanger

31925 (thermal), an ethylene / hexene copolymer was prepared. Ethylene was fed to the reactor at a rate of about 18.1 kg / hour (ie, about 40 lb / hr), hexene was fed into the reactor at a rate of about 0.27 kg / hour (ie, about 0.6 lb / hr), and further into the reactor fed hydrogen at a rate of 2.25 g / hour (ie 5 mPPH). Next, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (ie 5-8 PPH). The polymer production rate was about 12.15 kg / hour (ie, about 27 PPH). The reactor was equipped with an overpressure device set at 855 kg / hour (i.e. 1900 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). see U.S. Patent No. 5,693,727). A conical nozzle with an internal diameter of 0.10 cm (i.e. 0.041 inch) to inject the catalyst was placed in a gas stream in said pressurizing device. Solution containing 1 wt. % of catalyst A in toluene and a cocatalyst (which was MMAO-3A containing 1 wt% aluminum) were mixed directly on the production line before being injected into the fluidized bed using said nozzle (MMAO-3A is a solution of modified methylalumoxane in heptane, commercially available) from Akzo Chemicals, Inc. under the tradename Modified Methylalumoxane type 3A). The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 400: 1. As needed, nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. This procedure yielded a single-mode polymer having a nominal melt index I21 of 0.28 g / 10 minutes and a density of 0.935 g / cm ³ . The residual zirconium content, which was 1.63 ppmw, was calculated based on the mass balance of the reactor.

Example Section I - Comparative Example 2

In a 14.6 inch (35.6 cm) 14 inch gas phase polymerization reactor operating at 80 ° C, 2.2 megapascal (320 psig) and equipped with a water cooled exchanger

31925 / T n »e r r.-P r c c rt Γ.

of heat, an ethylene / hexene copolymer was prepared. Ethylene was fed to the reactor at a rate of about 19.8 kg / hour (ie, about 37 Ib / hour), hexene was fed into the reactor at a rate of about 0.18 kg / hour (ie about 0.4 Ib / hour), and then fed to the reactor fed hydrogen at a rate of 5.4 g / hour (ie 12 mPPH). Ethylene was fed to the reactor at a rate such that its partial pressure in the reactor was still 1.2 megapascal (i.e., 180 psig). The polymer production rate was about 11.25 kg / hour (ie, about 25 PPH). The reactor was equipped with a pressurizing device set at a power of 463.5 kg / hour (i.e. about 1030 PPH) of recycle gas (said pressurizing device being used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). A cone nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device. Solution containing 1 wt. % of Catalyst B in hexane was stirred for about 15 minutes in a 0.48 cm (3/16 inch) stainless steel tube with hexene at a rate of 0.09 kg / hour (ie 0.2 Ib / hour). The resulting mixture of Catalyst B and hexene was mixed directly with the cocatalyst (MMA0-3A containing 1 wt% aluminum) on the production line for about 40 minutes. In addition, isopentane and nitrogen were fed to the solution to control the average particle size of the resulting polymer. The whole system passed through the spray nozzle into the fluidized bed. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 300: 1. This gave a bimodal polymer having a melt flow index of 797 g / 10 minutes and a density of 0.9678 g / cm ³ . The residual zirconium content, which was 0.7 ppmw, was calculated based on the mass balance of the reactor. SEC analysis and deconvolution were performed using four powder distributions, the results of which are shown in Table I.

Example Section I - Example 3

In a 14.6 inch (35.6 cm) 14 inch gas phase polymerization reactor operating at 80 ° C, 2.2 megapascal (320 psig) and equipped with a water cooled exchanger

31925 / T

r. r f e r e r

r. eeecrrr C nrrr of heat, an ethylene / hexene copolymer was prepared. Ethylene was fed to the reactor at a rate of about 24 kg / hour (ie, about 53 Ib / hour), hexene was fed to the reactor at a rate of about 0.22 kg / hour (ie about 0.5 Ib / hour), and hydrogen was fed to the reactor. at a rate of 4 g / hour (ie 9 mPPH). Ethylene was fed to the reactor at a rate such that its partial pressure in the reactor was still 1.52 megapascal (ie 220 psig). The polymer production rate was about 11.25 kg / hour (ie, about 25 PPH). The reactor was equipped with an overpressure device set at a power of about 445.5 kg / hour (i.e. about 990 PPH) of recycle gas (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). A cone nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device. Solution containing 1 wt. % of Catalyst B in hexane was stirred for about 15 minutes in a 0.48 cm (3/16 inch) stainless steel tube with hexene at a rate of 0.09 kg / hour (ie 0.2 Ib / hour). The resulting mixture of Catalyst B and hexene was mixed directly on the production line with a cocatalyst (which was MMAO-3A containing 1 wt% aluminum) for about 20-25 minutes. In a separate stainless steel activation tube, a toluene solution containing 1 wt. % of Catalyst A was activated by MMAO-3A for about 50-55 minutes. The two independently activated solutions were mixed together for 4 minutes to form a single process catalyst stream. The amount of catalyst A in the feed solution was approximately 40 to 45 mol%. In addition, isopentane and nitrogen were fed to the solution to control the average particle size of the resulting polymer. The whole system passed through the spray nozzle into the fluidized bed. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 300: 1. This procedure yielded a bimodal polymer having a melt flow index of 0.045 g / 10 min and 10 min, respectively. 7.48 g / 10 minutes and having a density of 0.9496 g / cm ³ . The residual zirconium content that was

1.7 ppmw, was calculated based on the reactor mass balance. It was done

31925 / T r <c r c c c c. c c.

-f c C C- c r.

'r r - .c r r.

c · c c r SEC analysis and deconvolution using seven to eight powder distributions, the results of which are shown in Table I.

Example Section I - Example 4

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.2 megapascal (320 psig) and equipped with a water-cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 22.7 kg / hour (i.e., about 50 Ib / hour), hexene was fed into the reactor at a rate of about 0.32 kg / hour (ie, about 0.7 Ib / hour), and then fed to the reactor fed hydrogen at a rate of 4.95 g / hour (i.e. 11 mPPH). Ethylene was fed to the reactor at a rate such that its partial pressure in the reactor was still 1.52 megapascal (i.e. 220 psig). The polymer production rate was about 13.05 kg / hour (i.e., about 29 PPH). The reactor was equipped with an overpressure device set at 436.5 kg / hour (i.e. about 970 PPH) of recycle gas (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). A conical nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device. Solution containing 1 wt. % of Catalyst B in hexane was stirred for about 15 minutes in a 0.48 cm (i.e. 3/16 inch) stainless steel tube with hexene at a rate of 0.09 kg / hour (i.e., 0.2 lb / hour). The resulting mixture of Catalyst B and hexene was mixed directly on the production line with a cocatalyst (which was MMAO-3A containing 1 wt% aluminum) for about 20-25 minutes. In a separate stainless steel activation tube, a toluene solution containing 1 wt. % of Catalyst A was activated by MMAO-3A for about 50-55 minutes. The two independently activated solutions were mixed together for 4 minutes to form a single process catalyst stream. The amount of catalyst A in the feed solution was approximately 40 to 45 mol%. In addition, in order to control the average particle size of the resulting polymer,

31925 / T • rerer «f c. c isopentane and nitrogen. The whole system passed through the spray nozzle into the fluidized bed. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 300: 1. This procedure yielded a bimodal polymer having a melt flow index of 0.054 g / 10 min, respectively. 7.94 g / 10 minutes and having a density of 0.948 g / cm ³ . The residual zirconium content, which was 1.1 ppmw, was calculated based on the mass balance of the reactor. SEC analysis and deconvolution were performed using seven to eight distributions of powder, the results of which are shown in Table I.

Example Section I - Example 5

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.2 megapascal (320 psig) and equipped with a water-cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 27.2 kg / hour (ie about 60 Ib / hour), hexene was fed into the reactor at a rate of about 0.36 kg / hour (ie about 0.8 Ib / hour), and then fed to the reactor fed hydrogen at a rate of 5.85 g / hour (ie 13 mPPH). Ethylene was fed to the reactor at a rate such that its partial pressure in the reactor was still 1.52 megapascal (i.e. 220 psig). The polymer production rate was about 15.3 kg / hour (i.e. about 34 PPH). The reactor was equipped with an overpressure device set at a power of about 432 kg / hour (i.e. about 960 PPH) of recycle gas (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). A cone nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device. Solution containing 1 wt. % of Catalyst B in hexane was stirred for about 15 minutes in a 0.48 cm (i.e. 3/16 inch) stainless steel tube with hexene at a rate of 0.09 kg / hour (i.e., 0.2 lb / hour). The resulting mixture of Catalyst B and hexene was mixed directly on the production line with a cocatalyst (which was MMAO-3A containing 1 wt% aluminum) for about 20-25 minutes. In a separate stainless steel activation tube is toluene

31925 / T solution containing 1 wt. % of Catalyst A was activated by MMAO-3A for about 50-55 minutes. The two independently activated solutions were mixed together for 4 minutes to form a single process catalyst stream. The amount of catalyst A in the feed solution was approximately 40 to 45 mol%. In addition, isopentane and nitrogen were fed to the solution to control the average particle size of the resulting polymer. The whole system passed through the spray nozzle into the fluidized bed. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 300: 1. This procedure yielded a bimodal polymer having a melt flow index of 0.077 g / 10 min, respectively. 12.7 g / 10 minutes and having a density of 0.9487 g / cm ³ . The residual zirconium content, which was 0.9 ppmw, was calculated based on the mass balance of the reactor. SEC analysis and deconvolution were performed using seven to eight distributions of powder, the results of which are shown in Table I.

Example Section I - Example 6

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.2 megapascal (320 psig) and equipped with a water-cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 27.2 kg / hour (ie, about 60 Ib / hour), hexene was fed into the reactor at a rate of about 0.36 kg / hour (ie, about 0.8 Ib / hour) and fed to the reactor. fed hydrogen at a rate of 5.85 g / hour (ie 13 mPPH). Ethylene was fed to the reactor at a rate such that its partial pressure in the reactor was still 1.52 megapascal (i.e. 220 psig). The polymer production rate was about 15.3 kg / hour (i.e. about 34 PPH). The reactor was equipped with an overpressure device set at a power of about 495 kg / hour (i.e. about 1100 PPH) of recycle gas (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). A cone nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device.

31925 / T r. f e r. ô r. r r, -.

f r r r c r. r r r. f p. .- γρα r. , · ·· r r - p

Solution containing 1 wt. % of Catalyst B in hexane was stirred for about 15 minutes in a 0.48 cm (3/16 inch) stainless steel tube with hexene at a rate of 0.09 kg / hour (ie 0.2 Ib / hour). The resulting mixture of Catalyst B and hexene was mixed directly with the cocatalyst (MMAO-3A containing 1 wt% aluminum) on the production line for about 10-15 minutes. Toluene solution containing 1 wt. % of catalyst A was added to the activated catalyst B solution approximately 5 minutes before injection into the reactor. The amount of catalyst A in the feed solution was approximately 40 to 45 mol%. In addition, isopentane and nitrogen were fed to the solution to control the average particle size of the resulting polymer. The whole system passed through the spray nozzle into the fluidized bed. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 300: 1. This procedure yielded a bimodal polymer having a melt flow index of 0.136 g / 10 min, respectively. 38.1 g / 10 minutes and having a density of 0.9488 g / cm ³ . The residual zirconium content, which was 0.5 ppmw, was calculated based on the mass balance of the reactor. SEC analysis and deconvolution were performed using seven to eight distributions of powder, the results of which are shown in Table I.

Example Section I - Example 7

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 19.1 kg / hour (ie, about 42 Ib / hour), hexene was fed into the reactor at a rate of about 0.36 kg / hour (ie about 0.8 Ib / hour), and then fed to the reactor fed hydrogen at a rate of 5.85 g / hour (ie 13 mPPH). Ethylene was fed to the reactor at a rate such that its partial pressure in the reactor was still 1.52 megapascal (i.e. 220 psig). The polymer production rate was about 14.4 kg / hour (i.e., about 32 PPH). Said reactor was equipped with an overpressure device set at a power of about 904.5 kg / hour (i.e. about 2010 PPH) of recycle gas (said overpressure).

31925 / T o r p cc r c n r * c r c r f c fi r.

(ccr equipment is used in a fluidized bed gas phase polymerization reactor to form a polymer-poor zone). A cone nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device. A solution containing 0.25 wt. % of Catalyst B in hexane was mixed with hexene at a rate of 0.05 kg / hour (ie 0.1 lb / hour) in a 0.48 cm (3/16 inch) stainless steel tube. The resulting mixture of Catalyst B and hexene was mixed directly on the production line with a cocatalyst (MMAO-3A containing 1 wt% aluminum) for about 15 minutes. Toluene solution containing 0.5 wt. % of catalyst A was added to the activated catalyst B solution approximately 15 minutes before injection into the reactor. The amount of catalyst A in the feed solution was approximately 65 to 70 mole%. In addition, isopentane and nitrogen were fed to the solution to control the average particle size of the resulting polymer. The whole system passed through the spray nozzle into the fluidized bed. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 500: 1. This procedure yielded a bimodal polymer having a melt flow index of 0.06 g / 10 min and 10 min, respectively. 6.26 g / 10 minutes and having a density of 0.905 g / cm ³ . The residual zirconium content, which was 0.65 ppmw, was calculated based on the mass balance of the reactor. SEC analysis and deconvolution were performed using seven to eight distributions of powder, the results of which are shown in Table I.

31925 / T r r e e c * * r r c c r C or

Table I

Example 1 (cf.) 2 (cf.) 3 4 5 6 7 l ₂ i (g / 10 min) 0.28 on the 7.5 7.94 12.6 38.1 6.26 I21 / I2 - - 165.3 147 164.6 280.4 104 l ₂ (g / 10 min) without flow 797 0,045 0,054 0,077 0,136 0,060 Experimental SEC data M _n 80 600 2 952 7 908 10 896 10 778 10 282 8 700 M _w 407 375 13 398 340 011 263 839 259 389 261 138 287 961 MJM _n 5.05 4.54 43 24.2 24.1 25.4 33.10 M _n (off) - - 7 645 10 552 10 673 10 105 8 523 M _w (off) - - 339 752 258 282 248 215 252 310 284 814 MJMp (off) - - 44,44 24.48 23,26 24.97 33.42 LMW M _n (off) - 2 988 3 741 5 548 5 731 6 382 4 165 LMW ¹ M _w (off) - 13214 13 259 16 388 15214 18 333 11 771 LMW ¹ M _w / M _n -YYP) - 4.42 3.54 2.95 2.65 2.87 2.83 HMW M _n (off) 73 979 - 122 758 111 256 85 461 88 374 115 954 HMW ^Z M _w (off) 407 513 - 633 154 501 013 484 657 607 625 526 630 HMW ^Z Mw / Mn (off ·) 5.51 - 5.16 4.50 5.67 6.88 4.54 Share (HMW ^of ) 100.00 0.00 52,67 49.92 49.64 39.70 53,03

Table I - Completion

Example 1 (cf.) 2 (cf.) 3 4 5 6 7 Reactor conditions Temperature (° C) 85 80 80 85 85 85 85 Pressure C ₂ ^J (MPa 1.52 1.24 1.52 1.52 1.52 1.52 1.52 (Psi)) (220) (180) / 220) (220) (220) (220) (220) H2 / C2 molar ratio ³ 0.0016 0.0018 0.0013 0.0014 0.0014 0.0010 0.0019 Molar ratio c ₆ ⁴ / c ₂ ³ 0.00488 0.00153 0.0074 0.0073 0.0077 0.0075 0.0050 Delay time (hours) 3.6 7.5 5.3 4.74 3.87 3.87 3.4 Molar ratio hmw ² / lmw ¹ - * 0.71 0.73 0.76 0.76 2.16 Molar% Cat. A 100 - 41 42 43 43 68 Zr content by laboratory (ppm) - - 1.33 1.61 1.33 0.8 0.97 Zr content by injection (ppm) 1.63 - 1.46 1.06 0.9 0.54 0.62 average 1.63 - 1.40 1.34 1.12 0.67 0.80 Al / Zr molar ratio 400 - 330 380 320 307 500 Activity cat. B ^p - 9 965 12 515 18 754 37 288 50 142 Activity cat. A ^b 15 559 - 15 730 17 042 24 323 32 465 26 203

31925 / T • · r * e c e r «o»?

c ⁿ cr

Explanation to the table:

LMW = low molecular weight component

HMW = indication of the high molecular weight component

C ₂ = ethylene

C ₆ = hexene

5, 6 given in grams of polyethylene / millimole catalyst / hour

Comparative Examples 1 and 2 of Example I illustrate how a one-component catalyst system behaves. Examples 3 and 4, how changes in temperature will occur as long as the other conditions in the reactor and the catalyst feed system are substantially identical. It should be noted that when using a higher temperature, the value of the resulting polymer ratio M _w / M _{n is} lower, as is the melt flow rate (MFR). Examples 5 and 6 served to compare the effect of different catalyst activation arrangements under otherwise substantially identical conditions in the reactor and catalyst system. In the case of Example 6, it was then found that the overall activity of the catalyst was better. However, in this case, a smaller amount of high molecular weight material was produced. Examples 6 and 7 demonstrate the possibility of controlling the amount of high molecular weight material formed under substantially similar reactor conditions. In the case of Example 7, a higher amount of Catalyst A was injected into the reactor, and accordingly a larger amount of higher molecular weight material was also produced. Example Section I - Example 8

159 kg (350 pounds) of polyethylene produced according to Example 4 (hereafter referred to as polymer A) were mixed in a Werner Fleiderer ZSK-30 twin screw extruder with a melt temperature of 220 ° C with 1000 ppm Irganox® 1076 and 1500 ppm Irgafos® 1068 and formed into pellets. A 13 µm (0.5 mil) sheet was then blown from the pellets on an Alpine foil extrusion line. The film was produced under the following extrusion conditions: slot - triplex 160 mm, slot width 1.5 mm, temperature

31925 / T r r t r ft e ft r r. Γ r. yy yy yy yy yy ~ y,

Γ ft yyyy _c , r, r, f ^r · f 'i. ľ i.

rt e at 400 ° C, blown film width 122 cm (48 inches), target melting point 210 ° C (410 ° F) and extrusion speed - 144 kg / hour (310 Ib / hour), 191 kg / hour ( 420 lb / hr) and 209 kg / hr. (460 Ib / hr). For comparison, Escorene® HD7755.10 (which is a commercially available product from Exxon Chemical Company Houston, Texas, USA, manufactured in a series of reactors) was treated under the same conditions. All films were aged for 40 hours at 23 ° C 50% humidity. The properties of the individual films are summarized in Table IA.

Table IA

Polymer A HD 7755.10 Polymer A HD7755.10 Polymer A HD7755.10 Speed (kg / hr) (Ib / hr)) 144 (317) 144 (317) 191 (422) 191 (422) 209 (461) 209 (461) Foil thickness (pm (Mil)) 13 (0.524) 13 (0.502) 14 (0.532) 13 (0,519) 14 (0.543) 13 (0.528) Density (g / cm ^J ) .9489 0,949 .9502 0,949 0,9468 .9489 66 cm (26) arrow Day 1 (gram) ¹ 355 308 327 325 nm nm 66 cm (26 ”) arrow Day 7 (gram) ² 351 308 314 344 301 360 MD tear (g / pm (g / ml)) 0.87 (22) 0.63 (16) 0.98 (25) 0.59 (15) 0.87 (22) 0.59 (15) TD tear (g / pm (g / ml)) 3.82 (97) 4.02 (102) 3.03 (77) 3.31 (84) 3.94 (100) 3.19 (81) 1% MD (MPa (psig)) ⁵ sec 1 110 (161,000) 1 380 (200 200) 1 096 (159,000) 1 267 (183 800) 1 077 (156 200) 1 232 (178 700) 1% TD (MPa (psig)) ⁶ 1 272 (184 500) 1 465 (212 500) 1 127 (163 500) 1 425 (206 600) 1 113 (161 400) 1 465 (212 500) MD ultimate strength (MPa (psig)) ⁷ 100 14 445 99 14 347 87 (12 574) 104 (15 110) 89 (12 934) 108 (15 609) TD ultimate strength (MPa (psig)) ⁸ 92 13 369 84 (12 124) 74 (10 785) 85 12 278 81 (11 727) 79 (11 482) Ultimate elongation (%) 285 293 246 296 253 299 Ultimate elongation (%) 317 393 305 377 340 377 Haze {%) 59.6 64.0 57.8 62.0 56.9 60.9 45 ° Gloss 13.6 10.8 13.4 12.0 14.9 11.9

31925 / T

C β o r. r r. r r r c c r r r i · ft ft r r c r r - - -, r r J r. r

Explanation to the table:

MD = in machine direction; TD = in the transverse direction (i.e. perpendicular to the device direction)

Impact toughness tested by falling arrow on day 1 after foil production

Impact toughness tested by falling arrow on day 7 after foil production

3.4 Elmendorf tear resistance in machine direction (MD), transverse direction (TD)

5,6% 1 sec. modulus of elasticity determined as tangent to the stress-strain curve in the machine direction (MD), in the transverse direction

7.8 Ultimate tensile strength in machine direction (MD), transverse direction (TD)

Escorene® HD7755.10 is a linear polyethylene polymer manufactured using a dual reactor system, commercially available from Exxon Chemical Company, Houston, Texas, USA. The melt index I21 of this polymer is 7.5, the melt index ratio (MIR) is 125, the weight average molecular weight of the polymer is 180,000 and its density is 0.95 g / cm ³ .

Example Section I - Example 9

Several barrels of granulate samples (produced by the above-described polymerization method using a 2.3 (A: B) catalyst mixture A and B) were mixed in a drum with 1000 ppm Irganox® 1076, 1500 ppm Irgafos® 1068 and 1500 ppm calcium stearate The resulting mixture was pelletized at a temperature of 204 ° C (400 ° F) on a Prodex line with the resulting pellets having a size of 6.35 cm (2.5 "). said line was equipped with a single screw with a diameter of 50 mm, the length to diameter ratio of the extruder (L / D) was 18: 1 and the line

31925 / T e · e e c r e r. c r. f.

r r r tsa provided a 100 mm annular gap of 1 mm width. Extrusion was performed under the following conditions: slot temperature 204 ° C (400 ° F), line performance was 46 kg / hour (100 lbs / hour). A typical temperature profile was as follows:

193 ° C / 204 ° C / 204 ° C / 204 ° C / 204 ° C / 204 ° C / 210 ° C / 210 ° C (380 ° C / 400 ° C / 400 ° C / 400 ° C / 400 ° C / 400 ° C / 410 ° C / 410 ° C) for Drum 1 / Drum 2 / Block Adapter / Bottom Adapter / Vertical Adapter / Slot Bottom / Slot Center / Slot Top. The pellet samples were extruded to form a 25 µm (1.0 mil) film at a line speed of 48 cm / second (92 fpm) and a 13 µm (0.5 mil) film at a line speed of 94 cm / second ( 184 fpm) at a blow rate (BUR) of 4.0. In both cases, the resulting sleeve exhibited excellent stability with the typical bottleneck of the wine bottle. The deflated sleeve height (FLH) of the deflated sleeve was maintained at 91.4 cm (36 inches) for the 25 µm (1.0 ml) sheet, and for the 12.5 µm (0.5 mil) sheet, the line was maintained at 101.6 cm (40 inches). The pressure on the extrusion head and engine load were slightly higher than when extruding Escorene® HD7755.10 (which is a commercially available product from Exxon Chemical Company Houston, Texas, USA, manufactured in a series of reactors) under the same extrusion conditions. The properties of the resulting films are summarized in Table IB. All films were aged at 23 ° C for 40 hours. The impact strength tested with a 12.5 pp (0.5 mil) falling arrow of the film was 380 g, which is higher than that of the same film made from Escorene® HD7755.10, which was 330 g.

31925 / T e e c e e c e c r cc o

CC PC

Table IB

Escorene® 7755 Polymer B l ₂ (g / 10 minutes) 0.08 0,062 l ₂ i (g / 10 minutes) 10 10.02 l ₂₁ / l ₂ 134 160.5 Density (g / cm ^J ) 0,952 .9485 Output (kg / hour (Ib / hour)) 47 (100) '104 (48)

Table IB - continued

Escorene® 7755 Polymer B Slot flow rate (kg / hr (Ib / hr)) -3.6 (-8) - 3.6 (-8) Pressure on extrusion head (MPa (psig)) 50 (7 200) 53 (7 600) ' Engine load (amp) 56 61 Blow ratio (BUR) 4 4 Pour Line Height (FLH) (cm (inch)) 91.4 (36) 101.6 (40) 91.4 (36) 101.6 (40) Melt fracture not not not Sleeve stability good good good Extrusion speed (m / s (fpm)) 0.5 (92) 0,9- (185) 0.5 (92) 0.9 (184) Foil thickness (pm (mil)) 25 (1) 12.5 (0.5) 25 (1) 12.5 (0.5) Impact toughness (gram) 250 330 290 360 Tensile strength (MPa (psi)) MD 58 (8 400) 78 (11 300) 56 (8 100) 79 (11 400) TD 55 (7,900) 72 (10 400) 50 (7 230) 66 (9,520) Elongation (%) MD 350 230 410 330 TD 570 390 580 410 Elmendort tear resistance (g / pm (g / mil)) MD 0.98 (25) 0.87 (22) 0.95 (24) 1,30 (34) TD 5.59 (142) 2.83 (72) 8.07 (205) 2.80 (71) power ul of elasticity (MPa (psi)) MD 876 (127 000) 993 (144 000) 907 (131 500) 933 (135 350) TD 1,007 (146,000) 1,165 (169,000) 1,105 (160,250) 1,078 (156,300)

Example Section i - Example 10

By the same procedure as in Example 9, several barrels of granulate samples (polymer C produced by the above polymerization method using a 0.732 (A: B) mixture of catalysts and polymer D produced by the above polymerization method using a catalyst mixture of A and B in a ratio of 2.6 (A: B) was mixed in a drum with 1000 ppm Irganox® 1076, 1500 ppm Irgafos® 1068 and 1500 ppm calcium stearate.

31925 / T e β

The resulting mixtures were pelletized and extruded as described in Example 9. All films were aged for 40 hours at 23 ° C. The impact strength tested by a falling arrow of a film of 12.5 μητ (0.5 mil) was both for the film of polymer C and for the film of polymer D 380 g, which is higher than for the same film made from Escorene ® HD7755.10, when this parameter was 330 g. The data obtained are summarized in Table IC.

Table IC

sample Polymer C Polymer D Escorene® 7755 Reaction temperature (° C) 85 85 C ₂ (kPa (psi)) 1,517 (220) 1,517 (220) H ₂ / C ₂ molar ratio 0.0014 to 0.0016 0.0012 C ₆ / C ₂ molar ratio 0.0075 to 0.0078 0.00531 -0.00586 M _n 14 600 16 400 M _w  309 100 298 200 291 500 MVM _n 21.2 18.2 15.7 HMW / LMW 53.8 / 46.2 50.5 / 49.5 l ₂ (g / 10 min) 0,056 0,049 0.08 I ₂₁ (g / 10 minutes) 6.48 6.7 10 l ₂ i / l ₂ 115.8 138 134 Density (g / cm ^J ) .9487 .9461 0,952 Output (kg / hour (Ib / hour)) 46 (102) 46 (102) 45 (100) Slot flow ~ 3.6 (~ 8) ~ 3.6 (~ 8) ~ 4.5 (kg / hour (Ib / hour) Pressure on extrusion head 56 (8 120) 54 (7 890) 50 (7 230) (MPa (psig)) Engine load (amp) 64.5 63 59 Blow ratio 4 4 4 (BUR) Setting line height 101.6 (40) 101.6 (40) 91.4 (36) 101.6 (40) 91.4 (36) 101.6 (40) (FLH) (cm (inch)) Melt fracture not not not Sleeve stability satisfactory good good good good good Foil thickness (pm (mil)) 25.4 (1) 12.7 (0.5) 25.4 (1) 12.7 (0.5) 25.4 (1) 12.7 (0.5) Impact toughness (g) 200 380 200 380 250 330 Tensile strength (MPa (psi)) MD 71 137 68 107 58 78 (10,300) (19,900) (9,900) (15,500) (8 400) 11 300 TD 55 95 58 100 55 72 (7,900) (13,800) (8,400) (14,500) (7,900) (10,400)

31925 / T ft · ft · f · r · ft · ft · Γ /: C: · c / ft / ft · ft ·, ·, · ft; <c r. r «ftft r - r r '

Table IC - completion

sample Polymer C Polymer D Escorene® 7755 Elongation (%) MD 320 240 290 250 350 230 TD 630 385 610 350 570 390 Elmendorf tear resistance (g / μηη (g / mil)) MD 0.95 (24) 0.83 (21) 1.42 (36) 1.42 (36) 0.98 (25) 0.87 (22) TD 16.1 (410) 3.4 (87) 13.8 (350) 2,6 mm (66) 5.6 (142) 2,8 mm (72) Modulus of elasticity (MPa (psig) MD 724 (105) 827 (120) 710 (103) 758 (110) 876 (127) 993 (144) TD 883 (128) 869 (126) 889 (129) 786 (114) 1007 (146) 1165 (169)

Alpine line, 5.1 cm (2 inches) diameter screw, 10.2 cm (4 inches) diameter slot, 1 016 μηη (40 miles) slot width, 210 ° C (410 ° F) slot temperature.

The meaning of all abbreviations is the same as in the previous tables.

In addition to the examples described above, a number of other variants of the polymerization process using the catalyst systems described herein include the following:

Compound I can be dissolved in a solvent, preferably toluene, to form a solution of the desired concentration, which can then be used with other catalyst systems.

2. Catalyst A can be used as a solution in toluene at a concentration of 0.50 wt. % and catalyst B can be used as a 0.25 wt.% solution in hexane. %, i.e. at a molar ratio of B to A of about 0.7, when the two catalysts are activated separately and then mixed together (so-called parallel activation) or at a molar ratio of B to A of from 2.2 to 1.5 when catalyst A is first activated and then catalyst B (so-called sequential activation) is added.

3. Increase or decrease the reaction temperature in order to reduce or decrease the reaction temperature. extension of molecular weight distribution (M _w / M _n ).

4. Change the residence time to affect product properties. Major changes can have a significant impact. A residence time of from 1 to 5, preferably 4 hours, seems sufficient to produce a product with good properties.

31925 / T r c r r «-«. C ς <j f r r r r r c i r f r r · · r r. ,, · Yy yy. '* C r r

5. Spraying said catalyst into the reactor so as to form a polymer particle-poor zone. The polymer particle-poor zone can be formed at a flow rate of 22,500 kg / hour (50,000 lbs / hour) through a 15.24 cm diameter pipe. (6 inches). The catalyst can be atomized using a spray nozzle using nitrogen as the atomizing gas.

6. The activating agent, preferably MMAO 3A, can be used in the form of a solution in 7 wt% isopentane, hexane or heptane. %, the injection rate of which is sufficient to produce a ratio ΑΙ / Zr of from 100 to 300.

7. Catalyst A is mixed directly in the production line with ΜΑΟ 3A and then catalyst B is added directly to the resulting mixture directly on the production line. The whole mixture is then injected into the reactor.

8. Catalyst A is mixed directly in the production line with ΜΑΟ 3A, Catalyst B is also mixed directly on the production line with MMAO 3A, the two activated catalysts are mixed together directly on the production line, and the entire mixture is subsequently injected into the reactor.

The examples in Example Section II describe the use of a catalyst system comprising a catalytic metal compound comprising a Group 15 element of a Periodic Table of the Elements that contains benzyl leaving groups.

Example Section II. A mixed catalyst system comprising a metal catalyst comprising a Group 15 element of the Periodic Table of the Elements with benzyl leaving groups.

[(2,4,6-Me ₃ C ₆ H ₂ ) NHCH ₂ CH ₂ ] ₂ or (NH ligand) and {[(2,4,6-Me ₃ C ₆ H ₂ ) NCH ₂ CH ₂ ] ₂ NH } Zr (CH ₂ Ph) ₂ or (Zr-HN ₃ ) were prepared as described in Example I above.

Preparation of {[(2,4,6-Me ₃ C ₆ H ₂ ) NCH ₂ CH ₂ ] ₂ NH} ZrCl ₂ or (ZrCl ₂ -HN ₃ )

Zr (NMe ₂ ) ₄ was dissolved in a 250 mL round bottom flask in 50 mL pentane. To the solution was added 6.656 g (20.48 mmol) of [(2,4,6-Me ₃ C ₆ H ₂ ) NHCH ₂ CH ₂ ] 2NH as a solution in 50 mL of pentane, and the resulting solution was stirred for 2 hours. The formation of the mixed amide {[(2,4,6Me ₃ C ₆ H ₂ ) NCH ₂ CH ₂ ] 2N H Zr (NMe ₂ ) ₂ was shown by proton NMR, but this amide was not isolated from the mixture.

¹ H NMR (C ₆ D ₆ ) δ 6.94 (m, 4), 3.33 (m, 2), 3.05 (s, 6), 3.00 (m, 2), 2.59 ( m, 4), 2.45 (s, 6), 2.43 (s, 6), 2.27 (s, 6), 2.20 (s, 6), 1.80 (m, 1).

The solvent was removed in vacuo, the residue was dissolved in toluene, and 6.0 g (55 millimoles) of CISiMe ₃ was added in one portion. The solution was stirred for 24 hours, the solvent was removed in vacuo and the solids were suspended in pentane, collected by filtration and washed with pentane. 5.528 g (54%) of the desired dichloride was obtained, which was shown to be proton NMR.

¹ H NMR (C ₆ D ₆ ) δ 6.88 (s, 2), 6.81 (s, 2), 3.32 (m, 2), 2.86 (m, 2), 2.49 (s) s, 6), 2.47 (m, 4), 2.39 (s, 6), 2.12 (s, 6) the NH signal disappeared.

Preparation of Catalyst A (for the purposes of Example II)

In a 100 ml round bottom flask, to 2.051 g of methylalumoxane (MAO) (as 6.836 g of a 30 wt% solution in toluene, commercially available from Albeľmarle Corporation, Baton Rouge, Louisiana, USA) and 7,285 g of toluene added 0.145 g of ZrCl ₂ - HN ₃ . The resulting solution was stirred for 15 minutes, 5.070 g of silica (Davison 948, annealed at 600 ° C, available from WR Grace, Davison Division, Baltimore, Maryland, USA) was added thereto, and the mixture was thoroughly mixed. The mixture was then dried in vacuo overnight to give 7.011 g of a catalyst containing 0.36 wt. % zirconium and wherein the Al / Zr ratio was 122: 1.

Preparation of Catalyst B (for the purpose of Example II)

In a 100 ml round bottom flask, to 0.801 g of methylalumoxane (MAO) (as a 2,670 g solution in toluene at 30

31925 / T r- η r

rr, · _f r

Ir .-- r e c e r r r c c c c r r-f r. yyyy yyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy. %, which is commercially available from Albermarle Corporation, Baton Rouge, Louisiana, USA) and 4.679 g of toluene added 0.070 g of Zr - HN3. The resulting solution was stirred for 15 minutes, 2.130 g of silica (Davison 948, annealed at 600 ° C, available from W. R. Grace, Davison Division, Baltimore, Maryland, USA) was added thereto, and the mixture was thoroughly mixed. The mixture was then dried in vacuo overnight to give 2.899 g of a catalyst containing 0.35 wt. % zirconium and in which the ratio ΑΙ / Zr was 120: 1.

Example Section II - Comparative Example 1

Slurry polymerization of ethylene using Catalyst A

The polymerization was carried out in a 1 liter slurry polymerization autoclave reactor equipped with a mechanical stirrer, an outer water jacket to control the temperature, a septum inlet and outlet line, and a controlled dry nitrogen and ethylene feed. The reactor was dried and de-aired at 160 ° C. Then, 400 ml of isobutane, which served as solvent, was added to the reactor, and further, by means of an airtight syringe, 0.7 ml of a solution of trioctyl aluminum in hexane having a concentration of 25% by weight. % which served as a catcher. The reactor was heated to 90 ° C, 0.200 g of catalyst A was added thereto using pressurized ethylene, and the reactor was pressurized with ethylene to a pressure of 986 kilopascals (i.e. 143 psi). Polymerization was carried out for 40 minutes at a constant ethylene flow rate of 90 ° C and a pressure of 986 kilopascals (143 psi). The reaction was stopped by rapid cooling and depressurization. 10.5 g of polyethylene were obtained (F1 = no melt flow, catalyst activity = 209 g of polyethylene / millimolar catalyst / hour).

Example Section II - Example 2

Slurry polymerization of ethylene using Catalyst B

The polymerization was carried out in a 1 liter slurry polymerization autoclave reactor equipped with a mechanical stirrer, an outer water jacket to control the temperature, feed and

31925 / T · * f f f e f f f f r r <<<<r r r r ným · · · · · · ným · odvod ným ným ným ným odvod odvod ným ným ným odvod ným ným The reactor was dried and de-aired at 160 ° C. Then, 400 ml of isobutane, which served as solvent, was added to the reactor, and further, by means of an airtight syringe, 0.7 ml of a solution of trioctyl aluminum in hexane having a concentration of 25% by weight. % which served as a catcher. The reactor was heated to 90 ° C, 0.100 g of catalyst A was added thereto using pressurized ethylene, and the reactor was pressurized with ethylene to a pressure of 993 kilopascals (i.e. 144 psi). The polymerization was carried out for 30 minutes at a constant ethylene flow rate of 90 ° C and a pressure of 993 kilopascals (144 psi). The reaction was stopped by rapid cooling and depressurization. 11.8 g of polyethylene were obtained (F1 = no melt flow, catalyst activity = 641 g of polyethylene / millimole of catalyst / hour).

From the above, it follows that, under similar reaction conditions, a catalytic metal compound containing a Group 15 element and a leaving group which is a substituted hydrocarbon, preferably an alkyl substituted by an aryl group, has a much higher activity than the same halogen containing compound.

The examples in Example Section III describe the use of a catalyst system comprising an aluminum activator coupled to silica.

I

Example Section III. A mixed catalyst system comprising an oxide-coupled aluminum activating agent.

[(2,4,6-ME3C ₆ H 2) NHCH ₂ CH 2] 2 or (ligand) and {[(2,4,6Me ₃ C ₆ H 2) NCH ₂ CH 2] 2 NH} Zr (CH ₂ Ph) _2, or (Zr-HN ₃ ) were prepared as described in Example I above.

Preparation of aluminum bound to silica (Si-O-AI (C ₆ F5) 2)

A sample of 40.686 g of silica (Davison 948, annealed at 600 ° C and available from WR Grace, Davison Division, Baltimore, Maryland, USA) was suspended in a 500 mL round bottom flask in 300 mL of toluene. To the suspension was added 15.470 g (24.90 millimoles) of solid Al (C ₆ F ₅ ) ₃ as a solvate with one molecule of toluene and the resulting mixture was

31925 / T · - r e e · · f f o o <- - - <r r c or or or or or or or or -

was stirred for 30 minutes. The mixture was allowed to stand for 18 hours and the silica-bound aluminum was isolated by filtration and dried under vacuum for 6 hours to give 49.211 g of product. Al (C6F5) 3 · toluene was obtained as described in published European patent application EP 0 694 548, the contents of which are incorporated herein by reference. Preparation of Catalyst A (for the purpose of Example III)

To a suspension of 1,000 g of silica-bound aluminum (prepared in the above example) in 20 ml of toluene was added 0.076 g (0.124 mmol) of Zr-HN ₃ in 5 ml of toluene. The mixture was stirred for 30 minutes. The silica, which was colorless, turned orange-red. The silica was then isolated by filtration and dried under vacuum for 6 hours to give 1.051 g of product. The resulting transition metal concentration was 116 micromoles / gram catalyst.

Example Section III - Example 1

Slurry polymerization of ethylene and hexene using Catalyst A

The polymerization was carried out in a 1 liter slurry polymerization autoclave reactor equipped with a mechanical stirrer, an outer water jacket to control the temperature, a septum inlet and outlet line, and a controlled dry nitrogen and ethylene feed. The reactor was dried and de-aired at 160 ° C. Then, 400 ml of isobutane, which served as solvent, 35 ml of 1-hexene were added to the reactor, and then, using an airtight syringe, 0.7 ml of a solution of trioctyl aluminum in hexane, the concentration of which was 25 wt. % which served as a catcher. The reactor was heated to 60 ° C, 0.100 g of catalyst 3A was added thereto using pressurized ethylene, and the reactor was pressurized with ethylene to a pressure of 538 kilopascals (i.e. 78 psi). The polymerization was carried out for 30 minutes at a constant ethylene flow rate of 60 ° C and a pressure of 538 kilopascals (78 psi). The reaction was stopped by rapid cooling and depressurization. 70.0 g of copolymer were obtained (F1 = no melt flow, activity

31925 / T r- f ^r fcrrrrrrf C fr CC CC r

f. F C = ^f Catalyst 2320 g polyethylene / mmole katalyzátora.atm.hodina, the structure of the copolymer was introduced 10.5 wt. % 1-hexene).

The examples in Example IV describe the use of spraying a solution of a catalytic metal compound containing a Group 15 element.

Example Section IV. Injecting a solution of a catalytic metal compound containing a Group 15 element of the Periodic Table of the Elements.

[(2 ₁ 4,6-Me ₃ C ₆ H ₂ ) NHCH ₂ CH ₂ ] ₂ or (NH ligand or precursor of compound I) and {[(2,4,6-Me ₃ C ₆ H ₂ ) NCH ₂ CH ₂ ] ₂ NH } Zr (CH ₂ Ph) ₂ or (compound I) was prepared as above in Example section I.

Preparation of Catalyst A (for the purposes of Example IV)

A 1.5% catalyst solution in toluene was prepared by the following step sequence, all operations being carried out in a dry cabinet.

A 100 L purified toluene was weighed into a 1 L Erlenmeyer flask equipped with a Teflon coated stirrer. 7.28 g of tetrabenzyl zirconium were added to the toluene and the resulting solution was allowed to stir for 5 minutes.

during which time all solid dissolved. 5.42 g of compound I and a further 551 g of purified toluene were added to the solution. The mixture was allowed to stir for 15 minutes, whereupon all solid dissolved again. The resulting catalyst solution was transferred to a clean 1 liter Whitey cylinder, which was subsequently labeled, removed from the dry cabinet, and placed in a holder for preparation for later use.

Example Section IV - Example 1

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 18 kg / hr (i.e., about 40 lb / hr), and hexene was fed into the reactor.

31925 / T p fr t r f r f p I r c (·.

p * trrrciccr »rprrcrpprrerrrer <· r. ppr <· cpptr rc r '· (r C rp r - c, cr λ -, ·, _f .

0.3 kg / hr (i.e., about 0.6 lb / hr) and hydrogen was fed to the reactor at a rate of 2.25 g / hr (i.e., 5 mPPH). Next, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (ie 5-8 PPH). The polymer production rate was about 12.15 kg / hour (ie, about 27 PPH). The reactor was equipped with an overpressure device set at 855 kg / hour (i.e., 1900 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer-poor zone). see U.S. Patent No. 5,693,727). A cone nozzle with an inner diameter of 0.11 cm (i.e. 0.041 inch) to inject the catalyst was placed in a gas stream in said pressurizing device. Solution containing 1 wt. % of catalyst A in toluene and a cocatalyst (which was a solution of MMAO-3A in hexane containing 1 wt% aluminum) (MMAO-3A is a solution of modified methylalumoxane in heptane, commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A) were mixed directly on the production line before being injected into the fluidized bed using said nozzle. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 400: 1. As needed, nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. This procedure yielded a single-mode polymer having a nominal melt index I21 of 0.28 g / 10 minutes and a density of 0.935 g / cm ³ . The residual zirconium content, which was 1.63 ppmw, was calculated based on the mass balance of the reactor.

Example Section IV - Example 2

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 18 kg / hr (i.e., about 40 lb / hr), and hexene was fed into the reactor.

31925 / T λ »er (· <·» r - η ς _f · β rf. Rereeec ·> · 9 re ee r 9 rrr

C f ~ c r 9 f

C r .1 Γ «·. · Ll ·.

of the reactor was fed at a rate of about 1.6 kg / hr (i.e., about 3.5 lb / hr) and hydrogen was fed to the reactor at a rate of 11.25 g / hr (i.e., 25 mPPH). Next, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (ie 5-8 PPH). The polymer production rate was about 9 kg / hour (ie, about 20 PPH). The reactor was equipped with an overpressure device set at 855 kg / hour (i.e., 1900 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer-poor zone). see U.S. Patent No. 5,693,727). A cone nozzle with an inner diameter of 0.11 cm (i.e. 0.041 inch) to inject the catalyst was placed in a gas stream in said pressurizing device. Solution containing 1 wt. % of catalyst A in toluene was mixed directly with the 1-hexene 0.02 kg / h (i.e. 0.22 lb / h) and cocatalyst (MMAO-3A in isopentane solution containing 4 wt. % aluminum). The amount of MMAO catalyst was controlled such that the Al: Zr molar ratio was 746: 1. As needed, nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. Said unimodal polymer having nominal melt index l ₂ was 1.2 g / 10 min, ₂ l and 29.7 g / 10 min, the ratio of l ₂₁ / l ₂ was 23.9 and the density was 0 , 9165 g / cm ³ . The residual zirconium content, which was 0.89 ppmw, was calculated based on the reactor mass balance. Example Section IV - Example 3

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 105 ° C, 2.4 megapascal (350 psig) and equipped with a water-cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 18 kg / hour (ie, about 40 lb / hour), hexene was fed to the reactor at a rate of about 0.3 kg / hour (ie, about 0.6 lb / hour), and hydrogen was fed to the reactor. at a rate of 2.7 g / hour (ie

31925 / T rrreefrreeerr.>> Fc · cccc 7 rz (rc mPPH). Next, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (ie 5-8 PPH). The polymer production rate was about 10.8 kg / hour (ie, about 24 PPH). The reactor was equipped with an overpressure device adjusted to a power of about 720 kg / hour (ie about 1600 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). devices can be found in U.S. Patent No. 5,693,727). A cone nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device. A solution containing 1.5 wt. % of catalyst A in toluene and the cocatalyst (which was a solution of MMAO-3A in 25% heptane and 75% hexane containing 1.8 wt% aluminum) were mixed directly on the production line before being injected into the fluidized bed via said nozzle. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 320: 1. As needed, nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. This procedure yielded a single-mode polymer having a nominal melt index I21 of 0.67 g / 10 minutes and a density of 0.9358 g / cm ³ . The residual zirconium content, which was 2.33 ppmw, was calculated based on the mass balance of the reactor.

Example Section IV - Example 4

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 16.3 kg / hour (ie about 36 Ib / hour), hexene was fed into the reactor at a rate of about 1.6 kg / hour (ie about 3.5 Ib / hour), and then fed to the reactor fed hydrogen at a rate of 12.6 g / hour (ie 28 mPPH). Further, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (i.e., 5-8 PPH). Polymer production rate

31925 / T ccrrrrrrprtt * Γ r · f · c was approximately 8.1 kg / hour (ie approximately 18 PPH). The reactor was equipped with an overpressure device set at a power of about 855 kg / hour (i.e., about 1900 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). devices can be found in U.S. Patent No. 5,693,727). A cone nozzle with an inner diameter of 0.11 cm (i.e. 0.041 inch) to inject the catalyst was placed in a gas stream in said pressurizing device. Solution containing 1 wt. % of catalyst A in toluene was mixed directly with the 1-hexene 0.02 kg / h (i.e. 0.22 lb / h) and cocatalyst (MMAO-3A in isopentane solution containing 4 wt. % aluminum). The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 925: 1. As needed, nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. Said unimodal polymer having nominal melt index l and ₂ was 1.7 g / 10 min, ₂₁ l 41.7 g / 10 min, the ratio of l ₂₁ / l ₂ was 24.1 and the density was 0.917 g / cm ³ . The residual zirconium content, which was 0.94 ppmw, was calculated based on the mass balance of the reactor. Example Section IV - Example 5

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 18 kg / hour (ie, about 40 lb / hour), hexene was fed into the reactor at a rate of about 0.3 kg / hour (ie, about 0.6 lb / hour) and hydrogen was fed to the reactor. at a rate of 1.58 g / hour (i.e.

3.5 mPPH). Further, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (i.e., 5-8 PPH). The polymer production rate was about 9.9 kg / hour (i.e. about 24 PPH). The reactor was equipped with an overpressure device adjusted to a power of approximately 675 kg / hour (i.e. 1600

31925 / T • t · crrr * f F feerrofrcor r <· <- <nprc ^r crrpro ^r n C r <. Orr

PPH) (said pressurizing device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone. More information on the use of this type of device can be found in US Patent No. 5,693,727). A 0.11 cm (i.e., 0.041 inch) inner diameter cone nozzle for catalyst injection was placed in a gas stream in said pressurizing device. Solution containing 1 wt. % of catalyst A in toluene and the cocatalyst (which was a solution of MMAO-3A in hexane containing 1 wt% aluminum) were mixed directly on the production line before being injected into the fluidized bed by means of said nozzle. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 450: 1. Nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. Said unimodal polymer having nominal melt index l and ₂ was 0.10 g / 10 min and the density was 0.931 g / ^cm3. The residual zirconium content, which was 1.36 ppmw, was calculated based on the reactor mass balance.

Example Section IV - Example 6

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 18 kg / hour (ie about 40 lb / hour), hexene was fed into the reactor at a rate of about 0.23 kg / hour (ie about 0.5 lb / hour) and hydrogen was fed to the reactor. at a rate of 1.8 g / hour (ie 4 mPPH). Further, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (i.e., 5-8 PPH). The polymer production rate was about 9 kg / hour (i.e., about 20 PPH). The reactor was equipped with an overpressure device set at a power of approximately 922.5 kg / hour (ie 2050 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). type of device can

31925 / T e e r y r y r c

see U.S. Patent No. 5,693,727). A cone nozzle with an inner diameter of 0.11 cm (i.e. 0.041 inch) to inject the catalyst was placed in a gas stream in said pressurizing device. Solution containing 1 wt. % of catalyst A in toluene and the cocatalyst (which was a solution of MMAO-3A in isopentane containing 4 wt% aluminum) were mixed directly on the production line before being injected into the fluidized bed by means of said nozzle. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 1550: 1. Nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. Said unimodal polymer having nominal melt index of ₂₁ l was 0.36 g / 10 min and the density was 0.943 g / ^cm3. The residual zirconium content that was

2.5 ppmw, was calculated based on the reactor mass balance.

Example Section IV - Example 7

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 18 kg / hour (ie, about 40 lb / hour), hexene was fed into the reactor at a rate of about 0.3 kg / hour (ie, about 0.6 lb / hour) and hydrogen was fed to the reactor. at a rate of 5.4 g / hour (i.e., 12 mPPH). Further, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (i.e., 5-8 PPH). The polymer production rate was about 9 kg / hour (i.e., about 20 PPH). The reactor was equipped with an overpressure device set at a power of approximately 922.5 kg / hour (ie 2050 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). a device type can be found in U.S. Patent No. 5,693,727). A 0.11 cm (i.e., 0.041 inch) inner diameter cone nozzle to inject the catalyst was placed in a gas stream in said pressurizing device.

31925 / T r r r

100

Solution containing 1 wt. % of catalyst A in toluene and the cocatalyst (which was a solution of MMA0-3A in isopentane containing 4 wt% aluminum) were mixed directly on the production line before being injected into the fluidized bed by means of said nozzle. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 868: 1. As needed, nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. Said unimodal polymer having nominal melt flow rate was 3.5 l ₂₁ g / 10 min, ₂ l 0.115 g / 10 min, the ratio of l ₂₁ / l ₂ was 30.2 and the density was 0.949 g / cm ³ . The residual zirconium content, which was 2.5 ppmw, was calculated based on the mass balance of the reactor.

Example Section IV - Example 8

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 18 kg / hour (ie, about 40 lb / hour), hexene was fed to the reactor at a rate of about 0.495 kg / hour (ie, about 1.1 lb / hour), and hydrogen was fed to the reactor at 4 g / hour (i.e. 12 mPPH). Further, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (i.e., 5-8 PPH). The polymer production rate was about 11.25 kg / hour (i.e., about 25 PPH). The reactor was equipped with an overpressure device adjusted to a power of approximately 855 kg / hour (i.e. 1900 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer-poor zone). can be found in U.S. Patent No. 5,693,727). A 0.11 cm (i.e., 0.041 inch) inner diameter cone nozzle to inject the catalyst was placed in a gas stream in said pressurizing device. Solution containing 1 wt. % of catalyst A in toluene and a cocatalyst (which was a solution of MMAO-3A in isopentane containing 4 wt% aluminum) were mixed

31925 / T c e e

101 directly on the production line prior to spraying into the fluidized bed by means of said nozzle. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 842: 1. As needed, nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. Said unimodal polymer having nominal melt flow rate was ₂₁ l 41.2 g / 10 minutes, ₂ l 1.22 g / 10 min, and the ratio L ₂ / L ₂ was 33.8 and the density was 0.940 g / cm ³ . The residual zirconium content, which was 2.77 ppmw, was calculated based on the mass balance of the reactor.

Example Section IV - Example 9

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 90 ° C, 2.4 megapascal (350 psig) and equipped with a water-cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 21.6 kg / hour (ie, about 48 Ib / hour), hexene was fed into the reactor at a rate of about 0.3 kg / hour (ie about 0.6 Ib / hour), and then fed to the reactor fed hydrogen at a rate of 4.5 g / hour (ie 10 mPPH). Further, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (i.e., 5-8 PPH). The polymer production rate was about 10.35 kg / hour (i.e., about 23 PPH). The reactor was equipped with an overpressure device adjusted to a power of approximately 720 kg / hour (i.e. 1600 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer-poor zone). can be found in U.S. Patent No. 5,693,727). A cone nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device. A solution containing 1.5 wt. % of catalyst A in toluene and the cocatalyst (which was a solution of MMAO-3A in a mixture of 25% heptane and 75% hexane containing 1.8 wt% aluminum) were mixed directly on the production line before being injected into the fluidized bed using said nozzle. Quantity of MMAO

31925 / T

102 • c e • c r c r c r c r c r c c

CC r '' yyyy yy yyyyyyyyy

C «OC cr -r- fr - f · _r

C ^r . The catalyst was controlled so that the Al: Zr molar ratio was 265: 1. As needed, nitrogen and isopentane were fed to the feed nozzle to maintain a constant average particle size of the resulting polymer. Said unimodal polymer having nominal melt index l and ₂ was 0.3 g / 10 min and the density was 0.933 g / ^cm3. The residual zirconium content, which was 2.38 ppmw, was calculated based on the reactor mass balance.

Example Section IV - Example 10

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 95 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. Ethylene was fed to the reactor at a rate of about 20.25 kg / hour (ie, about 45 Ib / hour), hexene was fed to the reactor at a rate of about 0.3 kg / hour (ie about 0.6 Ib / hour), and then fed to the reactor fed hydrogen at a rate of 4.5 g / hour (ie 10 mPPH). Further, nitrogen was fed to the reactor at a rate of 2.25 to 3.6 kg / hour (i.e., 5-8 PPH). The polymer production rate was about 11.25 kg / hour (i.e., about 25 PPH). The reactor was equipped with an overpressure device adjusted to a power of approximately 720 kg / hour (i.e. 1600 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer-poor zone). can be found in U.S. Patent No. 5,693,727). A cone nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device. A solution containing 1.5 wt. % of catalyst A in toluene and the cocatalyst (which was a solution of MMAO-3A in a mixture of 25% heptane and 75% hexane containing 1.8 wt% aluminum) were mixed directly on the production line before being injected into the fluidized bed using said nozzle. The amount of MMAO catalyst was controlled so that the Al: Zr molar ratio was 350: 1. As needed, to maintain a constant average particle size of the resulting

31925 / T r

103 of the polymer introduced nitrogen and isopentane into the feed nozzle. Said unimodal polymer having nominal melt index l and ₂ was 0.4 g / 10 min and the density was 0.934 g / ^cm3. The residual zirconium content, which was 2.27 ppmw, was calculated based on the reactor mass balance.

For the sake of clarity, the data presented in Examples 1 to 10 of Example IV are again summarized in Table II.

Table II

Example Temperature ° C h ₂ / c ₂ b g / 10 min. bi g / 10 min. Density g / cm ³ Residual content Zr ppmw 1 85 0.0015 0.0043 on the 0.28 0,935 1.63 2 85 0,008 0.0410 1.2 29.7 0.9165 0.89 3 105 0.0015 0.0050 on the 0.67 .9358 2.33 4 85 0.0087 0.0450 1.7 41.7 0,917 0.94 5 85 0.0006 0.0051 on the 0.1 0,931 1.36 6 85 0.0023 0.0012 on the 0.36 0,943 2.50 7 85 0.0051 0.0013 0,115 3.5 0,949 2.50 8 85 0.0114 0.0154 1.22 41.2 0,940 2.77 9 90 0.0015 0.0050 on the 0.3 0,933 2.38 10 95 0.0015 0.0050 on the 0.4 0,934 2.27

Example Section IV - Example 11I

138 kg (300 pounds) of the polyethylene produced in Example 4 (referred to as polymer A) was mixed with a Werner-Fleiderer ZSK-30 twin screw extruder at a melt temperature of 200 ° C with 1000 ppm Irganox® 1076 and 1500 ppm Irgafos® 1068 and the resulting mixture was formed into pellets. A 25 µm (1.0 mil) sheet was blown from the pellets on a Gloucester extrusion line. The film was produced under the following extrusion conditions: line performance 85 kg / hour (188 Ib / hour), melt temperature 199 ° C (390 ° F), solidification line height 61 cm (24 inches), blow rate of 2.5 at slot width 1,524 pm (60 miles). For comparison, Escorene® HD7755.10 (a commercially available

31925 / T

104 ** ^r cfer r. eccetnccc

Exxon Chemical Company of Houston, Texas, USA, which is produced in a series of reactors). All films were aged for 40 hours at 23 ° C and 50% humidity. The properties of the individual films are summarized in Tables III and IV.

Table III

Example Escorene LL3002.32 Polymer A index melt flow 1.8 g / 10 min. Escorene LL3001.63 l ₂ (g / 10 min) 2 1 076 1 I21 / I2 29 24 27 Pellet density (g / cm ^J ) 0,918 0,918 0,918 Pressure on extrusion head (MPa ) Psig)) 19 (2,690) 17 (2,470) 23 (3,380) Engine load (%) 43 31.2 50.4 Foil thickness (μιτι (mil.)) 25 (1) 25 (1) 25 (1) Foil density (g / cm ^J ) 0,917 0,916 0,917 66 cm (26) arrow (gram) ¹ 136 168 149 MD pluck (g / pm (g / mil)) 12.7 (310) 10.4 (254) 9.1 (223) TD tear-off (g / μιτι (g / mil)) 24.9 (609) 25.7 (630) 30.7 (753) 1% MD (MPa (psig)) 210 (30,430) 218 (31 578) 216 (31,320) 1% TD (MPa (psig)) 269 (38.950) 290 (42 120) 274 (39 750) MD limit strength (MPa (psig)) 51 (7 444) 59 (8 552) 61 (8 880) TD ultimate strength (MPa (psig)) 45 (6 498) 68 (9 892) 48 (6,894) MD limit elongation (%) 641 546 552 Ultimate elongation TD (%) 793 694 756 45 ° gloss ⁴⁰ 79 23 Turbidity (%) 22 4.4 20

The meaning of each abbreviation is the same as in the previous tables.

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105 r · β

Table IV

Example Polymer A flow index melt 1.3 g / 10 min. Exceed® 350D60 l ₂ (g / 10 min) 1.35 1 I21 / I2 23 16 Pellet density (g / cm ^J ) 0,918 0,918 Pressure on extrusion head (MPa (psi)) 21 (3,010) 26 (3,810) Engine load (%) 37.2 56.7 Foil thickness (pm (mil)) 25 (1) 25 (1) Foil density (g / cm ³ ) 0,916 0,916 66 cm (26) arrow (gram) ¹ 276 646 MD pluck (g / pm (g / mil)) 8.9 (219) 10.8 (264) TD tear-off (g / pm (g / mil)) 25.1 (616) 16 (393) 1% MD secant (MPa (psi)). 214 (31 100) 200 (29 040) 1% TD (MPa (psig)) 286 (41,470) 228 (33 050) MD limit strength (MPa (psig)) 62 (9,017) 69 (9,986) TD ultimate strength (MPa (psig)) 53 (7 685) 59 (8 538) MD limit elongation (%) 529 504 Ultimate elongation TD (%) 690 646 45 ⁰ gloss 74 25 Turbidity (%) 5 23

The meaning of each abbreviation is the same as in the previous tables.

The examples in Example V describe the use of a feed solution of a mixed catalyst system comprising a catalytic metal compound comprising a Group 15 element and a sterically bulky ligand metallocene catalyst.

EXAMPLE V Injection of a mixed catalyst system solution comprising a catalytic metal compound containing a Group 15 element of the Periodic Table of the Elements and a sterically bulky ligand metallocene catalyst

Catalyst 1

31925 / T • e p r r r <· · r i i r c i i i i

106 ', - ^r -.,' From ^c

For the purposes of Example V, Catalyst 1 was indenylzirconium trispivalate, a metallocene compound with a sterically bulky ligand, prepared as described in Example I. Preparation of Catalyst 1 as a 1 wt. % f

All operations described below took place in a dry cabinet.

To a 1 L Erlenmeyer flask equipped with a Teflon-coated stirrer was charged 1 L of purified hexane. To the hexane was added 6.67 g of indenyl zirconium trispivalate as a dry powder. The resulting solution was allowed to stir for 15 minutes, during which time all solids dissolved. The resulting catalyst solution was transferred to a clean 1L Whitey cylinder, which was subsequently labeled, removed from the dry cabinet, and placed in a holder where it was ready for later use.

Catalyst 2

For purposes of the examples in Section 2, the catalyst, [(2,4,6Me3C6H2) NHCH2CH2] 2 NH ligand (or the ligand-1), and {[(2,4,6Me3C6H2) ₂ NCH 2] 2 NH} Zr (CH 2 Ph) 2 or (Compound I) prepared according to the procedures described in Example I above.

Preparation of Catalyst 2 in the form of a 1.5 wt.

%

All operations described below took place in a dry cabinet.

A 100 L purified toluene was weighed into a 1 L Erlenmeyer flask equipped with a Teflon coated stirrer. 7.28 g of tetrabenzyl zirconium were added to the toluene and the resulting solution was allowed to stir for 5 minutes, during which time all the solid dissolved. To the solution was added 5.42 g of ligand I as described above and an additional 551 g of purified toluene. The mixture was allowed to stir for 15 minutes, whereupon all solid dissolved again. The resulting catalyst solution was transferred to a clean 1L Whitey cylinder, which was subsequently labeled, removed from the dry cabinet, and placed in a holder where it was ready for later use.

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107 r.

Example Section V - Example 1

Ethylene / hexene was prepared in a 35.6 cm (14 inch) gas phase polymerization reactor operating at 85 ° C, 2.4 megapascal (350 psig) and equipped with a water cooled heat exchanger. copolymer. The reactor was equipped with an overpressure device set at 720 kg / hour (i.e. 1600 PPH) (said overpressure device is used in a fluidized bed gas phase polymerization reactor to form a polymer particle-poor zone). see U.S. Patent No. 5,693,727). A cone nozzle with an internal diameter of 0.14 cm (i.e., 0.055 inch) for catalyst injection was placed in the gas stream in said pressurizing device. Prior to catalyst injection, the ethylene pressure was about 1.5 megapascal (i.e., about 220 psig), the 1-hexene concentration was about 0.3 molar%, and the hydrogen concentration was about 0.12 molar%.

Catalyst 2 solution was diluted with toluene to a concentration of 0.5 wt. % and this solution was injected into the reactor at a rate of 12 cm ³ / hour. The cocatalyst (which was MMAO-3A containing 1 wt% aluminum) was mixed with catalyst 2 directly in the pipeline before being injected into the reactor, with a molar ratio of ΑΙ / Zr of 400: 1. The polymer production rate was approximately 10.9 kg / hour ( ie approximately 24 PPH). Further, 2.3 kg / hour (5.0 lb / hr) of nitrogen, 0.05 kg / hour (0.1 lb / hr) of 1-hexene and 0.09 kg / hour (0.2 L / hr) were fed to the spray nozzle. Ib / hour) of isopentane. The resulting polymer had a melt index of 0.31 and a density of 0.935 g / cm ³ . After formation of the polymer, the flow rate of catalyst 2 was reduced to 6 cm ³ / hour and a feed solution of 13 cm ³ / hour was fed with a solution of catalyst 1 in hexane at a concentration of 0.125 wt. %. The whole order of mixing was that first hexene and MMAO were mixed with catalyst 1, where catalyst solution 2 was added to the mixture, followed by addition of isopentane and nitrogen to the resulting mixture. The ΙΙ / Zr ratio in the whole system described above was approximately 500. Within 6 hours after the start of catalyst 1 addition,

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108 ft ft

Γ r ft r ft

^{R r} r, c.

bimodal polymer having nominal melt index l and ₂ was 12.9 g / 10 min, flow index ratio of the melt (MFR) l ₂₁ / l ₂ was 130, and the density was 0.953 g / ^cm3. The average particle size of the resulting polymer was 0.12 cm (i.e., 0.0479 inches). The residual zirconium content, which was 0.7 ppmw, was determined by X-ray fluorescence spectroscopy.

The contents of all documents cited above, priority documents and / or documents describing the test methods are incorporated herein by reference. As will be apparent from the foregoing general description and from the description of particular embodiments of the present invention, many changes may be made to the specific procedures described above without departing from the scope of the invention. The present invention also encompasses the use of two or more metal compounds comprising a Group 15 element together with one or more sterically bulky ligand metallocene catalyst compounds and / or one or more conventional catalyst systems. Accordingly, it is not intended to limit the scope of the present invention in any way.

Claims (43)

PATENT CLAIMS r r r. C A process for the polymerization of one or more olefins, characterized in that said polymerization is carried out in the presence of a catalyst system comprising a catalytic metal compound comprising a Group 15 element of the Periodic Table of the Elements. The method of claim 1, wherein said catalyst system further comprises a sterically bulky ligand metallocene catalyst compound, a conventional transition metal catalyst compound, or a mixture thereof. Method according to any one of the preceding claims, characterized in that said catalytic metal compound comprising a Group 15 element is a Group 3 to 14 catalytic metal compound in which said metal is bound to a bidentate or a tridentate ligand comprising an element of group 15 of the Periodic Table of the Elements. The method of any one of the preceding claims, wherein said hafnium catalyst compound comprising a Group 15 element of the Periodic Table of the Elements is a Group 3 to 14 Group catalytic metal compound in which said metal is bound to at least to one leaving group and to at least two of the 15 atoms of the 15th group, at least one of the at least two of the 15 atoms of the 15th group is bound to the 15 or 16 group element wherein said bridging structure is preferably selected from the group consisting of a hydrocarbon group containing from 1 to 20 carbon atoms, a group containing a heteroatom, a silicon atom, germanium, tin, lead and phosphorus. 5. The method of claim 4, wherein said atom of an element of Group 15 or Group 16 is not further bound thereto. 31925 110 c c Ô Ô e e e e e o o o o o r. or is also bonded to a hydrogen atom, a member of a group 14 element of the Periodic System, a halogen atom, to a group containing a heteroatom, each of the two member atoms of 15. The moiety of the Periodic Table of the Elements is also bonded to the cyclic group and optionally may be bonded to a hydrogen atom, a halogen atom, a heteroatom, or a hydrocarbon group or a heteroatom-containing group. or A method according to any one of the preceding claims, characterized in that said catalytic metal compound comprising a Group 15 element of the Periodic Table of the Elements is a compound of formula (I) or (II): I // R ⁶ Z ^R1 - ^Y \ R3-L-MX _{n + m} R R ² -Z R4 R ⁶ R5 R7 (I) where: M _r3 _ \, / ^y \ R ³ - L γ M ⁿ X n_2 \ t / R7 R ⁵ : id is a Group 3 to 14 metal atom, preferably Group 3 to 7 metal atom, more preferably Group 4 to 6 metal atom, are leaving groups, which may be the same or different, y is 0 or 1, n is the oxidation state of the metal M, m is the formal charge of YZL or YZL, L is an atom of an element of Group 15 or 16 of the Periodic Table of Elements, 31925 / T f- 111 * r c f c r r · c r r *; C Γ C ·. . · R c r r ·? r r 'f r ·' -o. ·. L is an atom of an element of the 15th or 16th group of the Periodic System of Elements or a group containing an atom of an element of the 14th group of the Periodic System of Elements, Y is an atom of an element of group 15 of the Periodic Table of the Elements, l Z is an element of the 15th group of the Periodic System of Elements, R ¹ and R ² are independently selected from the group consisting of a hydrocarbon group containing from 1 to 20 carbon atoms, a heteroatom containing up to 20 carbon atoms, a silicon atom, a germanium atom, a tin atom, a lead atom or a phosphorus atom, R ³ is absent or selected from the group consisting of a hydrocarbon group, a hydrogen atom, a halogen atom, a heteroatom-containing group, R ⁴ and R ⁵ are independently selected from the group consisting of alkyl, aryl, substituted aryl, cyclic alkyl, substituted cyclic alkyl, cyclic arylalkyl, substituted cyclic arylalkyl, and a polycyclic system, wherein R ¹ and R ² may be joined together and / or R ⁴ and R ⁵ may be joined together, R ⁶ and R ⁷ are not independently present or are independently selected from the group consisting of hydrogen, alkyl, halogen, heteroatom, and hydrocarbon, and R * is either absent or selected from the group consisting of hydrogen, a group containing an atom of an element of the 14th group of the Periodic Table, a halogen atom and a group containing a heteroatom. Process according to Claim 6, characterized in that the groups R ⁴ and R ⁵ represent groups of the general formula 1: 31925 / T 112 R12 R ⁸ R ⁹ Binding to Z or Y where: R ⁸ to R ¹² are independently selected from the group consisting of hydrogen, alkyl of from 1 to 40 carbon atoms, halogen, heteroatom, heteroatom containing up to 40 carbon atoms, preferably from the group consisting of linear or branched alkyl containing from 1 to 20 carbon atoms, preferably a methyl group, an ethyl group, a propyl group or a butyl group, or any two of R ⁸ to R ¹² may together form a cyclic group and / or a heterocyclic group, wherein said cyclic groups may be aromatic. The process according to claim 7, characterized in that the groups R ⁹ , R ¹⁰ and R ¹² represent independently of one another a methyl group, an ethyl group, a propyl group or a butyl group or the groups R ⁹ , R ¹⁰ and R ¹² represent a methyl group and R ⁸ and R ¹¹ represent hydrogen atoms. A process according to any one of claims 6 to 8, characterized in that the groups L, Y and Z independently represent a nitrogen atom; R ¹ and R ² are hydrocarbon groups, R ³ is a hydrogen atom, and R ⁶ and R ⁷ are absent or L and Z are independently nitrogen, L is a hydrocarbon group, and R ⁶ and R ⁷ are absent . The method of any one of the preceding claims, wherein said metal catalyst compound comprising a Group 15 element of the Periodic Table of Elements comprises at least one substituted hydrocarbon leaving group containing six or more carbon atoms, wherein the at least one substituted hydrocarbon group is 31925 / T c e r y r y c 113 yy yy C · r Γ. preferably an aryl-substituted alkyl group, which is most preferably a benzyl group. The process according to any one of the preceding claims, wherein said catalyst system further comprises one or more activating agents. Process according to any one of the preceding claims, characterized in that said catalyst compounds and / or said activating agents are injected in a liquid carrier into a gas phase or slurry polymerization reactor. 13. The process of claim 12, wherein a gas-phase polymerization reactor is used in which at least two catalysts and at least one activating agent are injected in the liquid carrier, each of said catalysts being activated independently and catalysts and the activating agents are mixed together in said liquid carrier before being injected into the reactor. 14. The process of claim 13 wherein said catalysts are activated sequentially. 15. The method of claim 13, wherein: (i) said catalysts are mixed together in a liquid carrier and subsequently one or more activating agents are added to said liquid carrier; or (ii) said catalysts are mixed together in a liquid carrier and subsequently fed to a distribution device connected to a liquid carrier. and then one or more activating agents are fed to said distribution device, said activating agents being fed to said device both at the same site as the catalysts and at a completely different site. A process according to any one of claims 12 to 15, wherein said liquid carrier comprising one or more catalysts. 31925 / T 114 p e c y, y r y c y y y y y y y y y, y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y. ij The one or more activating agents are fed to a device for injecting said liquid carrier into the reactor. . 17. The process of claim 16 wherein said catalysts and the liquid carrier are introduced into said reactor for injecting the liquid carrier into the reactor rather than the activating agent. The method of claim 12 or 17, wherein said liquid carrier comprises a liquid stream flowing or sprayed into the reactor. Process according to any one of claims 12 to 18, characterized in that at least one catalyst, at least one activating agent and a liquid carrier are fed to a reactor injection device into which, after the first catalyst and the activating agent are introduced, another catalyst (s) is fed. s). 20. The method of claim 12, wherein: i) a first composition comprising at least one catalyst in a liquid carrier is fed to a device which is connected to the reactor, the second composition containing at least one activating agent in the liquid carrier is fed to the same device, then another after a certain time is added to said device a catalyst in a liquid carrier and the resulting mixture of catalysts and at least one activating agent is injected into the reactor; or ii) at least one catalyst (a) and at least one activating agent (a) are mixed together in the liquid carrier, at least one catalyst (b) and at least one activating agent (b) is mixed together in a liquid carrier, wherein the catalyst (b) is different from the catalyst (a) and / or the activating agent (b) is different from the activating agent (a), and then both mixtures are fed to the apparatus which is connected to the reactor and subsequently injected together into the reactor; or iii) a liquid carrier comprising the catalyst (b) and the activating agent (b) are fed to a device which is connected to 31925 / T r ρ r r 115 of the device, a liquid carrier comprising catalyst (a) and activating agent (a), or iv) a first composition comprising at least one catalyst (a), at least one activating agent (a) and a liquid carrier is placed in a device that is attached to the reactor, then a second composition comprising at least one catalyst (b), at least one activating agent (b) and a liquid carrier is fed to the same apparatus, wherein the catalyst (b) and / or the activating agent (b) is different from the catalyst (a) and / or activating agent (a), and subsequently the mixture of both compositions is injected into the reactor, or v) at least one catalyst and a liquid carrier are placed in a reactor injection device and further catalyst (s) and activating agent (s) are fed to the device; or vi) a first composition comprising at least one catalyst (s), at least one catalyst (s); the activating agent (a) and the liquid carrier are placed in a reactor injection device, then a second catalyst in the liquid carrier is fed to the same device, followed by a second activating agent in the liquid carrier and the entire mixture is injected into the reactor. The method according to claim 12, characterized in that said catalyst compounds and / or said activating agents are mixed together prior to incorporation into a liquid carrier and / or said carrier is an alkane, preferably selected from the group consisting of pentane, hexane and / or isopentane. Process according to any one of claims 1 to 11, characterized in that said catalyst compounds and / or activating agents are supported on one or more supports. 31925 / T r c 116 23. The method according to claim 22, characterized in that the activator is selected from the group consisting of alkyl aluminum compound, alumoxanes, modified alumoxanes, non-coordinating anions, boranes, borate ionizing compound and / or aluminum-containing Lewis acid of formula VII, ^1: R _n AI (ArHal) ₃ - _n (VII) where: R is a mono-anionic ligand, ArHal is a halogenated aromatic group having 6 carbon atoms or a polycyclic aromatic group having a higher number of carbon atoms or a group containing aromatic rings in which two or more rings (or fused ring systems) are attached directly to each other, and n is 1 or 2, preferably 1 . A process according to any one of the preceding claims, characterized in that the process is carried out continuously in the gas phase or continuously in suspension. The process according to any one of the preceding claims, wherein said olefin is ethylene or propylene or a mixture of ethylene and at least one additional monomer containing from 3 to 20 carbon atoms. 26. A catalyst system comprising a catalytic metal compound comprising a Group 15 element, an activating agent, and optionally a carrier. 27. The catalyst system of claim 26, further comprising a sterically bulky ligand metallocene catalyst compound, a conventional transition metal catalyst compound, or a mixture thereof. 28. The catalyst system of claim 26 or 27, wherein said metal catalyst compound comprising the element of 15. 31925 / T * e ΛΓΟ f yy r. r <· c F r r n C r r. r ť,. c r i - r ti c n - <- λ r. r r · · g r r · Group 117 of the Periodic Table of the Elements is a catalytic metal compound of Group 3-14 of the Periodic Table in which said metal is bound to a bidentate or tridentate ligand containing an element of Group 15 of the Periodic Table of Elements . Catalyst system according to any one of claims 26 to 28, characterized in that said metal catalyst compound comprising a Group 15 element and said sterically bulky ligand metallocene catalyst compound, if present, are contacted with a catalyst. with an activating agent to form a reaction product which is subsequently contacted with a carrier. The catalyst system deposited according to any one of claims 26 to 29, wherein the catalyst system is supported and said activating agent is an aluminum-containing Lewis acid of formula VII: R @ ₁ Al (ArHal) ₃ . _n (VII) where: R is a mono-anionic ligand, ArHal is a halogenated aromatic group having 6 carbon atoms or a polycyclic aromatic group having a higher number of carbon atoms or a group containing aromatic rings in which two or more rings (or fused ring systems) are attached directly to each other, and n is 1 or 2, preferably 1 . Use of a Group 3 to 14 metal catalyst compound comprising a Group 15 element for producing a high molecular weight polymer that is a component of a multimodal polymerization mixture. 31925 / T 118 t ft e r c r r c e r C t r n C <r c r c c ft c C CC c c c ft f r o Use of a catalytic, sterically bulky metallocene compound for the production of a low molecular weight polymer component of a multimodal polymerization mixture. 33. The method of claim 2, wherein said sterically bulky ligand metallocene compound is a compound of Formula VI: L ^D MQ ₂ (YZ) X _n (VI) wherein: M is a Group 3 to 16 metal atom, preferably a Group 4 to 6 transition metal atom, 1 ^D sterically bulky metal ligand M, preferably an indenyl or fluorenyl group, and Q are all independently bonded to metal M, Q ₂ (YZ) forms a single-charge polydentate ligand, X is a monovalent anionic group when n equals 2 or a divalent anionic group when n equals 1, n is 1 or 2. 34. The process of claim 33 wherein X is the carbamate, carboxylate, or other heteroalkyl group described by the combination of QYZ. The method of claims 2 and 33, wherein the molar ratio of said metal compound comprising a Group 15 element to the sterically bulky ligand metallocene compound is in the range of 1: 99 to 99: 1, preferably in the range of from 20: 80 to 80: 20. 36. A polymer produced by the process of claims 2 and 33 to 35, characterized in that a density of from about 0.89 to 0.97 g / cm ³ and / or the melt index of ₂₁ l is from 1 to 10 g / 10 minutes or less and / or whose melt index ₁₂ is from about 0.01 to 1000 31925 / T 119 g / 10 minutes and / or whose melt index ratio I21 / I2 is 80 or more and / or whose weight average molecular weight M _w is 180,000 or more and / or which contains less than 100 ppm ash and / or which contains nitrogen containing ligand detectable by high resolution mass spectroscopy. 37. An ethylene-based polymerization composition, characterized in that it is produced in a single reactor using at least two catalysts, its melt index ratio I21 / I2 is greater than 80, contains less than 100 ppm ash and / or the density of said polyethylene is 0,945 g / cm ³ or more. The polymerization composition of claim 37, wherein it is extrudable at a rate of about 2.8 kg / hour / cm (i.e., about 17 Ib / hour / inch) of the gap circumference. 39. The polymerization composition of claim 37, wherein the film made from said composition having a thickness of 13 µm (5 mils) has a haze of 60% or less and has a gloss degree of 45 ° at 13 degrees, said film being the blown or flat film and / or said film having a thickness of 13 µm (0.5 mils) preferably has a tear resistance in the machine direction (MD) ranging from about 0.20 g / µm (ie about 5 g / mil) to 1 µm. 0 g / pm (ie 25 g / ml). 40. An ethylene polymer or copolymer, characterized in that it contains 2,0 ppm or less of residual zirconium, its melt index I21 is equal to or less than 12 g / 10 minutes, its melt flow ratio I21 / I2 equals or is greater than 80 and / or contains 2.0 ppm or less of residual nitrogen and / or contains less than 100 ppm of ash. A film selected from the group consisting of extruded, blown or flat film, characterized in that it is produced from a polymer produced by the process of claim 12. 42. A composition comprising polyethylene produced by the process of claim 12 having a density in the range of 0.910 g / cm &lt; ^{3 &gt;} to 0.935 31925 / T 120 g / cm ³ , its melt index is 10 g / 10 minutes or less, its haze is 10% or less, and its gloss at 45 ° is 60 units or more. 43. A composition comprising polyethylene produced by the method of claim 42, wherein said polyethylene has a density ranging from 3 3 ' 0.915 g / cm to 0.930 g / cm, its melt index is 5 g / 10 minutes or less, and / or its haze is 7% or less, and / or its 45 ° gloss is 75 units or more, and / or its falling arrow impact strength (determined in accordance with ASTM D 1709 Method A) is 150 g or more and / or its Elmendorf tear resistance in the machine direction is 100 g or more and / or its Elmendorf tear resistance in the transverse direction is 500 g or more.