KR20020060956A - Catalyst Compositions, Methods of Polymerization, and Polymers Therefrom - Google Patents

Abstract

The present invention relates to a mixed catalyst composition comprising a catalyst composition comprising a Group 15-containing metal compound, a Group 15-containing metal compound and a second metal compound, preferably a bulky ligand metallocene catalyst, useful in a polymerization reaction process, Unsupported and supported catalyst systems, and methods of polymerizing olefin (s) using them. The invention also relates to novel polyolefins, generally polyethylenes, in particular multimodal polymers and more particularly bimodal polymers and their use in various end uses such as films, shaped bodies and pipes.

Description

Catalyst Compositions, Methods of Polymerization, and Polymers Therefrom < RTI ID = 0.0 >

Advances in polymerization and catalysis have provided the possibility to produce a large number of new polymers with improved physical and chemical properties useful in a wide variety of superior products and applications. The development of new catalysts has greatly expanded the choice of polymerization reaction-form (solution, slurry, high pressure or vapor phase) to produce specific polymers. In addition, advances in polymerization techniques have provided a more efficient, highly productive and economically improved method. In particular, a specific example of such an advance is the development of a technique that utilizes a bulky ligand metallocene catalyst system.

More recently, development has led to the discovery of anionic multidentate heteroatomic ligands as mentioned in the following references: (1) Kempe et al., "Aminopyridinato ligands - New Directions and Limitations", 80 ^th Canadian Society for Chemistry Meeting, Windsor, Ontario, Canada, June 1-4, 1997; (2) Kempe et al., Inorg. Chem. 1996, vol 35 6742; (3) Jordan et al of polyolefin catalysts based on hydroxyquinolines (Bei, X .; Swenson, DC; Jordan, RF, Organometallics 1997, 16 , 3282); (4) Horton, et al., "Cationic Alkylzirconium Complexes Based on a Tridentate Diamide Ligand: New Alkene Polymerization Catalysts", Organometallics, 1996, 15, 2672-2674, to tridentate zirconium complexes; (5) Baumann, et al. , "Synthesis of Titanium and Zirconium Complexes that Contain the Tridentate Diamido Ligand [((t-Bu-d 6) NOC 6 H 4) 2 O] 2- {[NON} 2-) and The Living Polymerization of 1-Hexene by Activated [NON] ZrMe2 ", Journal of the American Chemical Society, Vol. 119, pp. 3830-3831; (6) Cloke et al, " Zirconium Complexes incorporating the New TridentateDiamide Ligand [(Me 3 Si) N {CH 2 CH 2 N (SiMe 3)} 2] 2- (L);. The Crystal Structure of [Zr (BH ₄ ) ₂ L] and [ZrCl {CH (SiMe ₃ ) ₂ } L] ", J. Chem. Soc. Dalton Trans, pp. 25-30, 1995; . (7) Clark et al, "Titanium (IV) complexes incorporating the aminodiamide ligand [(SiMe 3) N {CH 2 CH 2 N (SiMe 3)} 2] 2- (L); the X-ray crystal structure of [TiMe ₂ (L)] and [TiCl {CH (SiMe ₃ ) ₂ } (L)], Journal of Organometallic Chemistry, Vol. 50, pp. 333-340, 1995; (8) Scollard et al., &Quot; Living Polymerization of alpha-olefins by Chelating Diamide Complexes of Titanium ", J. Am. Chem. Soc., Vol. 41, pp. 10008-10009,1996; And (9) Guerin et al., &Quot; Conformationally Rigid Diamide Complexes: Synthesis and Structure of Titanium (IV) Alkyl Derivatives ", Organometallics, Vol. 15, No. 24, pp. 5085-5089, 1996.

U.S. Patent No. 5,576,460 describes a process for preparing an arylamine ligand, and U.S. Patent No. 5,889,128 discloses an initiator having a ligand having metal atoms and two Group 15 atoms and Group 16 atoms or three Group 15 atoms A living polymerization method of used olefins is described. EP 893 454 A1 also describes preferably titanium transition metal amide compounds. In addition, U.S. Patent No. 5,318,935 describes a catalyst system for producing amido transfer metal compounds, and in particular isotactic polypropylene. Polymerization catalysts containing bidentate and tridentate ligands are also described in U.S. Patent No. 5,506,184.

Traditional bulky ligand metallocene catalyst systems produce polymers that are more difficult to process into film using, for example, old-fashion extruders in some situations. One technique for improving these polymers is to blend them with other polymers for the purpose of creating blends with the desired properties that each component may have separately. Although the two polymer blends tend to be more processable, they add a blending step that is expensive and interferes with the manufacturing / processing process.

Higher molecular weights lead to the desired polymer mechanical properties and stable bubble formation during film formation. However, this property also inhibits extrusion processing by increasing the backpressure in the extruder, promoting melt fracture defects in the expandable bubble, and potentially promoting a degree of orientation that is too high in the processed film . Anionic multisite heteroatom-containing catalyst systems tend to produce very high molecular weight polymers. In order to improve this, it is possible to reduce the extruder back pressure and inhibit melt fracture by forming a minor amount of a low molecular weight polymer component. Several industrial processes are based on this principle using a number of reactor technologies to produce bimodal molecular weight distribution (MWD) high density polyethylene (HDPE) products that can be processed. Mitsui Chemicals HDPE product HIZEX ™ is regarded as a worldwide standard. HIZEX ™ is produced in two or more costly reactor processes. In a number of reactor processes, each reactor produces a single component of the final product.

It has also been attempted in the art to produce two polymers simultaneously in the same reactor using two different catalysts. PCT patent application WO 99/03899 describes the production of bimodal polyolefins using a typical bulky ligand metallocene catalyst and a conventional form of Ziegler-Natta catalyst in the same reactor. However, the use of two different types of catalysts results in polymers with characteristics that can not be anticipated from the characteristics of the polymer that can be produced when each catalyst is used separately. This unpredictability arises, for example, from competition or other effects between the catalyst or catalyst system used.

High density and high molecular weight polyethylene are useful in film applications where high stiffness, excellent toughness and high throughput are required. Such polymers are also useful in pipe applications where rigidity, toughness and long term durability, and particularly resistance to environmental stress cracking, is required.

Accordingly, there is a need for a combination of catalysts capable of producing a reformable catalyst compound and, preferably, a processable polyethylene polymer in a single reactor having the desired combination of processing, mechanical and optical properties.

The present invention relates to a catalyst composition comprising a Group 15-containing metal compound and to a mixed catalyst composition comprising at least two metal compounds. Preferably, at least one of the metal compounds of the mixed composition is a Group 15-containing metal compound. More preferably, the other metal compound is a bulky ligand metallocene catalyst compound. The present invention also relates to catalyst systems using catalyst compositions, their use in olefin (s) polymerization. The present invention also relates to the use of the novel polyolefins, generally polyethylenes, in particular multimodal polymers, and more particularly bimodal polymers, and their use in a variety of end uses such as films, will be.

Fig. 1 is a diagram of Example 1 described below.

Fig. 2 is a diagram of Example 2 below. Fig.

3 is a diagram of Example 3 below.

4 is a diagram of Example 4 below.

5 is a diagram of Example 5 below.

6 is a diagram of Example 6 below.

7 is a diagram of Example 7 below.

8 is a diagram of Example 8 below.

9 is a diagram of Example 9 below.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The present invention relates to the use of the Group 15-containing metal catalyst compound in the polymerization of olefin (s). In addition, the inventors have now found that the 15 group-containing catalyst compounds can be used in combination with other catalysts, preferably bulky ligand metallocene compounds, to produce new bimodal MWD HDPE products. Surprisingly, the mixed catalyst composition of the present invention can be used in a single reactor system.

Group 15-containing metal compounds

Group 15-containing compounds are generally group 3 to group 14 bound to at least one leaving group and also to at least two Group 15 atoms, at least one of which is also bonded to Group 15 or Group 16 atoms via another group, Include groups 3 to 7, more preferably groups 4 to 6, and more preferably group 4 atoms.

In one embodiment, at least one Group 15 atom is also bonded to a Group 15 or Group 16 atom through a C ₁ to C ₂₀ hydrocarbon group, a heteroatom-containing group, silicon, germanium, tin, Group 15 or group 16 atom is not bonded to anything or bonded to a hydrogen, a Group 14 atom-containing group, a halogen or a heteroatom-containing group, and each of the two Group 15 atoms is also a hydrogen, a halogen, a heteroatom A cyclic group which may optionally be bonded to the hydrocarbyl group, or a heteroatom-containing group.

In one embodiment, the Group 15-containing metal compound of the present invention is represented by the formula (I) or (II)

In this formula,

M is a Group 3 to Group 12 transition metal or Group 13 or Group 14 metal, preferably a Group 4, Group 5 or Group 6 metal, more preferably a Group 4 metal, most preferably zirconium, titanium or Hafnium;

Each X is independently a leaving group, preferably an anionic leaving group, more preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen, most preferably an alkyl;

y is 0 or 1 (when y is 0, no L 'group is present);

n is an oxidation state of M, preferably +3, +4 or +5, more preferably +4;

m is a formal charge of YZL or YZL 'ligand, preferably 0, -1, -2 or -3, more preferably -2;

L is a Group 15 or Group 16 element, preferably nitrogen;

L 'is a Group 15 or Group 16 element or Group 14-containing group, preferably carbon, silicon or germanium;

Y is a Group 15 element, preferably nitrogen or phosphorus, more preferably nitrogen;

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

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

R ³ is absent or is a linear, cyclic or branched alkyl group having a hydrocarbon group, a hydrogen, a halogen, a heteroatom-containing group, preferably a carbon atom of 1 to 20 carbon atoms, more preferably R ³ is absent , Hydrogen or an alkyl group, most preferably hydrogen;

R ⁴ and R ⁵ independently represent an alkyl group having preferably not more than 20 carbon atoms, more preferably 3 to 10 carbon atoms, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, More preferably a C ₁ to C ₂₀ hydrocarbon group, a C ₁ to C ₂₀ aryl group or a C ₁ to C ₂₀ aralkyl group, or a heteroatom- Containing group, for example PR ₃ , wherein R is an alkyl group;

R < ¹ > and R < ² > may be interconnected (to each other) with respect to each other, and R < ⁴ > and R < ⁵ >

R ⁶ and R ⁷ are independently not present or are a hydrogen, an alkyl group, a halogen, a heteroatom or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group having from 1 to 20 carbon atoms, more preferably present Not;

R ^* is absent or is hydrogen, a Group 14 atom-containing group, a halogen, a heteroatom-containing group.

&Quot; Formal charge of YZL or YZL 'ligand " means the charge of the entire ligand in which the metal and leaving group X are absent.

&Quot; R ¹ and R ² can also be interconnected " means that R ¹ and R ² can be directly bonded to each other, or bonded to each other through another group. &Quot; R ⁴ and R ⁵ may also be interconnected " means that R ⁴ and R ⁵ may be directly bonded to each other, or may be bonded to each other through another group.

The alkyl group may be a straight or branched alkyl radical or an alkenyl radical, an alkynyl radical, a cycloalkyl radical or an aryl radical, an acyl radical, an ayl radical, an alkoxy radical, an aryloxy radical, an alkylthio radical, a dialkylamino radical, Alkyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight-chain, branched or cyclic alkylene radicals, or the radicals of these radicals, Lt; / RTI > Aralkyl groups are defined as substituted aryl groups.

In a preferred embodiment, R < ⁴ > and R < ⁵ > are independently a group of the formula:

Wherein R ⁸ to R ¹² are each independently selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group, a halide, a heteroatom, a heteroatom-containing group containing up to 40 carbon atoms, preferably a C ₁ to C ₂₀ straight or branched Branched alkyl group, preferably a methyl, ethyl, propyl or butyl group, and two R groups may form a cyclic group and / or a heterocyclic group. The cyclic group may be aromatic. In preferred embodiments, R ⁹ , R ¹⁰ and R ¹² are independently a methyl, ethyl, propyl or butyl group (including all isomers), and in preferred embodiments R ⁹ , R ¹⁰ and R ¹² are methyl groups and R ⁸ and R ¹¹ is hydrogen.

In a particularly preferred embodiment, R ⁴ and R ⁵ are both groups represented by the following formula:

In these embodiments, M is a Group 4 metal, preferably zirconium, titanium or hafnium, more preferably zirconium; L, Y and Z are each nitrogen; R ¹ and R ² are each -CH ₂ -CH ₂ -; R ³ is hydrogen; R ⁶ and R ⁷ are absent.

In a preferred embodiment, at least one X is a substituted hydrocarbon group, preferably a substituted alkyl group having at least 6 carbon atoms, most preferably an aryl-substituted alkyl group. The most preferred aryl-substituted alkyl group is benzyl.

In a particularly preferred embodiment, the Group 15-containing metal compound is a compound (I) represented by the formula:

In the above formula, Ph represents phenyl.

The Group 15-containing metal compounds of the present invention are useful in the prior art as described in EP 0 893 454 A1, U.S. Patent No. 5,889,128 and U.S. Patent No. 5,889,128, all of which are incorporated herein by reference And is produced by a known method. U.S. Patent Application Serial No. 09 / 312,878, filed May 17, 1999, describes a gas or slurry phase polymerization method using supported bisamide catalysts, which is also incorporated herein by reference.

The preferred direct synthesis of these compounds is carried out in the presence of a neutral ligand (see, for example, the formula I or < RTI ID = 0.0 > II YZL or YZL ') and M ⁿ X _n where M is a Group 3 to Group 14 metal and n is the oxidation state of M and each X is an anionic group such as a halide, The reaction is carried out at about 150 ° C (preferably 20 ° C to 100 ° C), preferably for at least 24 hours, and then the mixture is treated with an excess (for example, 4 equivalents or more) of alkylating agent such as methylmagnesium bromide in ether . The magnesium salt is removed by filtration, and the metal complex is separated by standard techniques.

In one embodiment, the Group 15-containing metal compound is reacted with a neutral ligand (YZL or YZL ' of the reference example, formula I or II) in a non-saturated or polar solvent with a compound of the formula M ⁿ X _n, Wherein n is an oxidation state of M and each X is an anionic leaving group such as a halide at a temperature of about 20 캜 or higher, preferably about 20 캜 to about 100 캜 Followed by treatment of the mixture with an excess of an alkylating agent followed by recovery of the metal complex. In a preferred embodiment, the solvent has a boiling point of 60 占 폚 or higher, such as toluene, xylene, benzene, and / or hexane. In yet another embodiment, the solvent consists of an ether and / or methylene chloride, whichever is preferred.

Bulky ligand metallocene compound

In one embodiment, the Group 15-containing metal compound may be combined with a second metal compound to form a mixed catalyst composition. The second metal compound is preferably a bulky ligand metallocene compound.

Generally, bulky ligand metallocene catalyst compounds include hlaf or full sandwich compounds having one or more bulky ligands bonded to at least one metal atom. Representative bulky ligand metallocene compounds are generally defined as containing one or more leaving group (s) and one or more bulky ligand (s) bonded to at least one metal atom. In one preferred embodiment, at least one bulky ligand is? Bonded to a metal atom, most preferably? ⁵ -bonded to a metal atom.

The bulky ligand is generally represented by one or more open, acyclic or fused ring (s) or ring system (s), or combinations thereof. These bulky ligands, preferably ring (s) or ring system (s) are typically comprised of atoms selected from Group 13 to Group 16 atoms of the Periodic Table of the Elements, preferably the atoms are carbon, nitrogen, oxygen, , Phosphorus, germanium, boron and aluminum, or combinations thereof. Most preferably, the ring (s) or ring system (s) is selected from cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similar functional ligand structures such as pentadiene, cyclooctatetraendiyl, But are not limited to, carbon atoms, such as carbon atoms, carbon atoms, and ligands. The metal atom is preferably selected from Group 3 to Group 15 of the Periodic Table of the Elements and lanthanum or actinide. Preferably the metal is a transition metal selected from Groups 4 to 12, more preferably from Groups 4, 5, and 6, and most preferably the transition metal is selected from Group 4.

In one embodiment, the bulky ligand metallocene catalyst compound is represented by the formula III:

L ^A L ^B MQ _n

Wherein M is a metal atom selected from the Periodic Table of Elements and may be a Group 3 to Group 12 metal or may be selected from the lanthanum or actinide family of the Periodic Table of Elements and preferably M is a transition metal of Group 4, , More preferably M is a Group 4 transition metal, and still more preferably M is zirconium, hafnium or titanium. The bulky ligands L ^A and L ^B are open, acyclic or fused ring (s) or ring system (s) and are unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom-substituted And / or an ancillary ligand system including a heteroatom-containing cyclopentadienyl-type ligand. Non-limiting examples of bulky ligands include cyclopentadienyl ligand, cyclopentaphenanthrenyl ligand, indenyl ligand, benzindenyl ligand, fluorenyl ligand, octahydrofuranyl ligand, cyclooctatetraendiyl ligand, cyclopenta (WO 99/40125), pyrrolyl ligand, pyrazolyl ligand, carbazolyl ligand, borabenzene ligand, and the like, as well as cyclododecene ligands, azulenyl ligands, azulene ligands, phthalene ligands, Hydrogenated versions thereof, such as tetrahydroindenyl ligands. In one embodiment, L ^A and L ^B are bonded η-, preferably η ³ M in the M-may be any other ligand structure capable of binding-binding, and most preferably η ^5. In another embodiment, the atomic molecular weight (MW) of L ^A or L ^B is at least 60 amu, preferably at least 65 amu. In yet another embodiment, L ^A and L ^B together with the carbon atoms are optionally substituted with one or more heteroatoms such as nitrogen, silicon, boron, germanium, sulfur and phosphorus to form open, acyclic or preferably fused To form a ring or ring system, for example a heterocyclopentadienyl subligand. Other L ^A and L ^B bulky ligands include bulky amides, phosphides, alkoxides, aryl oxides, imides, carbides, borolides, porphyrins, phthalocyanines, corins and other polyazomarkocycles , But are not limited to these. Independently, each L ^A and L ^B may be the same or different types of bulky ligands bound to M. In one embodiment of formula III, only one of L ^A or L ^B is present.

Independently, each L ^A and L ^B may be unsubstituted or substituted by a combination of substituent groups R. Non-limiting examples of the substituent group R include hydrogen, or a linear or branched alkyl radical, or an alkenyl radical, an alkynyl radical, a cycloalkyl radical or an aryl radical, an acyl radical, an ayl radical, an alkoxy radical, an aryloxy radical, Or a pharmaceutically acceptable salt thereof, wherein the compound is selected from the group consisting of a radical, a dialkylamino radical, an alkoxycarbonyl radical, an aryloxycarbonyl radical, a carbamoyl radical, an alkyl- or dialkyl-carbamoyl radical, an acyloxy radical, an acylamino radical, A cyclic alkylene radical, or a combination thereof. In a preferred embodiment, the substituent group R has not more than 50 non-hydrogen atoms, preferably 1 to 30 carbons, which may also be substituted by halogen or heteroatoms. Non-limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like and all isomers thereof such as tert-butyl, do. Other hydrocarbyl radicals include hydrocarbyl radicals including fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like. Substituted organometalloid radicals; And halocarb-substituted organometalloid radicals including tris (trifluoromethyl) -silyl, methyl-bis (difluoromethyl) silyl, bromomethyldimethyl germyl and the like; And disubstituted boron radicals including, for example, dimethylboron; And disubstituted pnictogen radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen (s) including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide chalcogen) radicals. Non-hydrogen substituents R include, but are not limited to, olefinically unsaturated substituents including vinyl-terminated ligands such as but-3-enyl, prop-2-enyl, hex- Silicon, boron, aluminum, nitrogen, phosphorus, sulfur, tin, sulfur, germanium and the like. In addition, at least two R groups, preferably two adjacent R groups are combined to form a ring structure having 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron or combinations thereof do. Further, the substituent group R group such as 1-butanyl can form a carbon sigma bond to the metal M. [

Other ligands may be bonded to the metal M as at least one leaving group Q. In one embodiment, Q is a monoanionic labile ligand having a sigma-bond to M. Depending on the oxidation state of the metal, the value for n may be 0, 1 or 2 such that the above formula III represents a neutral bulky ligand metallocene catalyst compound.

Non-limiting examples of Q ligands include amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, weak bases such as hydrides or halogens, or combinations thereof. In another embodiment, two or more Qs form part of a fused ring or ring system. Other examples of Q ligands include but are not limited to cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, ), Dimethyl amide, dimethyl phosphide radical, and the like, and includes substituents for R as described above.

In one embodiment, the bulky ligand metallocene catalyst compound of the present invention comprises a compound of formula (IV) wherein L ^A and L ^B are bridged to each other by at least one bridging group A,

L ^A AL ^B MQ _n

The crosslinked compounds represented by these formula IV are known as crosslinked bulky ligand metallocene catalyst compounds. L ^A , L ^B , M, Q and n are as defined above. Non-limiting examples of bridging group A include at least one bridging group, often referred to as a bivalent moiety such as, but not limited to, at least one of carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atoms, Include bridging groups containing Group 13 to 16 atoms. Preferably the bridging group A contains carbon, silicon or germanium atoms, most preferably A contains at least one silicon atom or at least one carbon atom. The bridging group A may also contain a substituent group R as defined above including halogen and iron. Non-limiting examples of bridging group A is hydroxy R _'2 C, R' ₂ Si, R _'2 SiR' ₂ Si, R _'2 Ge, may be represented by R'P, where R' is independently hydride, Substituted hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organic metalloid, halocarb-substituted organic metalloid, disubstituted boron, disubstituted phynthoguan, substituted chalcogen or halogen Or two or more of R < 1 > may combine to form a ring or ring system. In one embodiment, the crosslinked bulky ligand metallocene catalyst compound of formula IV has two or more bridging groups A (EP 664 301 B1).

In one embodiment, the bulky ligand metallocene catalyst compound is a compound wherein the R substituents on the bulky ligands L ^A and L ^B of formulas III and IV are replaced by the same or different numbers of substituents on each bulky ligand. In another embodiment, the bulky ligands L ^A and L ^B of formulas III and IV are different from each other.

Other bulky ligand metallocene catalyst compounds and catalyst systems useful in the present invention are disclosed in U.S. Patent Nos. 5,064,802, 5,145,819, 5,149,819, 5,276,208, 5,296,034, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398, 5,753,578, 5,854,363, 5,856,547, 5,858,903 , 5,859,158, 5,900,517 and 5,939,503 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11445, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 And WO 99/14221 and European patent publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP -B1-0 632 819, EP-B1-0 748 821 and EP-B1-0 757 996, all of which are incorporated herein by reference in their entirety.

In one embodiment, bulky ligand metallocene catalyst compounds useful in the present invention include bridged heteroatom mono-bulky ligand metallocene compounds. These types of catalysts and catalyst systems are described, for example, in PCT Publication Nos. WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO 96/00244, WO 97/15602 and WO 99/20637 and U.S. Patent Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405, and European Patent Publication EP-A-0 420 436, all of which are incorporated herein by reference in their entirety.

In this embodiment, the bulky ligand metallocene catalyst compound is represented by the following formula V:

L ^C AJMQ _n

Wherein M is a Group 3 to Group 16 metal atom or a metal selected from Actinium and Lanthanum of the Periodic Table of the Elements, preferably M is a Group 4 to Group 12 transition metal, more preferably M is 4, 5 or 6 Group transition metal, most preferably M is a Group 4 transition metal, in particular any titanium, in any oxidation state; L ^C is a substituted or unsubstituted bulky ligand bound to M; A is attached to M and J; J is a heteroatom moiety ligand; A is a bridging group; Q is a monovalent anionic ligand; n is an integer of 0, 1 or 2; In formula V, L ^C , A and J form a fused ring system. In one embodiment, L ^C of formula V is as defined above for L ^A , and A, M and Q of formula V are as defined above in formula III.

In formula (V), J is a heteroatom-containing ligand, wherein J is an element of coordination number 3 selected from Group 15 or an element of coordination number 2 selected from Group 16 of the Periodic Table of Elements. Preferably J is nitrogen, phosphorus, oxygen or sulfur and nitrogen is most preferred.

In another embodiment of the present invention, the bulky ligand metallocene-type catalyst compound is a heterophasic ligand wherein the bulky ligand, ring (s) or ring system (s) comprises one or more heteroatoms, Is a click ligand complex. Non-limiting examples of heteroatoms include Group 13 to Group 16 elements, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus and tin. Examples of these bulky ligand metallocene catalyst compounds are described in WO 96/33202, WO 96/34021, WO 97/17379, WO 98/22486 and WO 99/40095 (dicarbamoyl metal complexes) and EP-A1-0 874 005 And U.S. Patent Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417 and 5,856,258, all of which are incorporated herein by reference.

In one embodiment, the bulky ligand metallocene catalyst compound is a pyridine or quinoline residue as described in U.S. Patent Application Serial No. 09 / 103,620, filed June 23, 1998, which is incorporated herein by reference. ≪ / RTI > is a complex known to be a transition metal catalyst based on a bidentate ligand containing a bidentate ligand. In another embodiment, the bulky ligand metallocene catalyst compounds are those described in PCT publications WO 99/01481 and WO 98/42664, both of which are incorporated herein by reference in detail.

In another embodiment, the bulky ligand-type metallocene catalyst compound is prepared as described in U.S. Patent Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057, both of which are incorporated herein by reference in greater detail Metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted pi-bonded ligand, and a complex of one or more heteroalyl moieties.

It is also contemplated that any of the bulky ligand metallocene catalyst compounds of the present invention have at least one fluoride or fluorine-containing leaving group as described in U.S. Patent Application Serial No. 09 / 191,916, filed November 13, 1998 .

In another embodiment, the other metal compound or the second metal compound is a bulky ligand metallocene catalyst compound represented by the following formula VI:

L ^D MQ ₂ (YZ) X _n

Wherein M is a Group 3 to Group 16 metal, preferably a Group 4 to Group 12 transition metal, and most preferably a Group 4, 5 or 6 transition metal; L ^D is a bulky ligand bound to M; Each Q is independently bonded to M and Q < ₂ > (YZ) forms a ligand, preferably a single charged multidentate ligand; A or Q is a monovalent anionic ligand also bonded to M; when n is 2, X is a monovalent anionic group, or when n is 1, X is a divalent anionic group; n is 1 or 2;

In formula VI, L and M are as defined above for formula III. It was about Q has the formula III as defined above, preferably Q is -O-, -NR-, -CR ₂ - and is selected from the group consisting of -S-; Y is C or S; Z is in case of _{-OR, -NR 2, -CR 3,} -SR, -SiR 3, -PR 2, -H, and substituted or is selected from the group consisting of unsubstituted aryl groups, with the proviso that Q is -NR- Z is selected from the group consisting of -OR, -NR ₂ , -SR, -SiR ₃ , -PR _2, and -H; R is selected from the group comprising carbon, silicon, nitrogen, oxygen, and / or phosphorus, preferably wherein R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably alkyl, An aryl group; n is an integer from 1 to 4, preferably 1 or 2; when n is 2, X is a monovalent anionic group, or when n is 1, X is a divalent anionic group; Preferably, X is carbamate, carboxylate, or any other heteroalyl moiety represented by the combination of Q, Y, and Z.

In a particularly preferred embodiment, the bulky ligand metallocene compound is represented by the formula:

In the mixed catalyst system, the first and second metal compounds are mixed in a ratio of 1: 1000 to 1000: 1, preferably 1:99 to 99: 1, more preferably 10:90 to 90:10, : 80 to 80:20, still more preferably 30:70 to 70:30, even more preferably 40:60 to 60:40. The particular ratios selected depend on the desired end product and / or activation method.

Activator and activation method

The above-described metal compounds are generally activated in various ways to obtain a catalyst compound having a vacant coordination site for coordinating, interpolating and polymerizing olefins.

In the present patent specification and the appended claims, the term " activator " refers to compounds or components capable of activating the Group 15-containing metal compounds and / or bulky ligand metallocene catalyst compounds of the present invention as described above, or Method. Non-limiting examples of activators include, for example, neutral bulky ligand metallocene catalyst compounds or Group 15-containing metal compounds with catalytically active Group 15-containing metal compounds and / or bulky ligand metallocene cations A Lewis acid or non-ionic satellite ionizable or ionizing activator that can be converted, or other compounds including Lewis bases, aluminum alkyls, cocatalysts of the conventional type, and combinations thereof. The use of alumoxane or modified alumoxane as the activator and / or the addition of tri (n-butyl) ammonium tetrakis (triphenylphosphine), which can ionize the neutral bulky ligand metallocene catalyst and / or Group 15- (Pentafluorophenyl) boron, trisperfluorophenylboron metalloid precursor or trisperfluoronaphthyl fluoride metalloid precursor, polyhalogenated heteroborane anion (WO 98/43983), or combinations thereof. It is also within the scope of the present invention to use ionizing activators.

In one embodiment, an activation method using an ionizing ionic compound that does not contain an active proton but can produce a Group 15-containing metal compound cation or a bulky ligand metallocene catalyst cation and their non-satiety anions is also included , EP-A-0 426 637, EP-A-0 573 403 and U.S. Patent No. 5,387,568, all of which are incorporated herein by reference.

There are a variety of methods for making alumoxane and modified alumoxane, and non-limiting examples of these are 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, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 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, 5,856,256 and 5,939,346 and EP-A-0 561 476, EP-B1-0 279 586, EP- 594 218 and EP-B1-0 586 665 and PCT Publication No. WO 94/10180, all of which are incorporated herein by reference in their entirety.

Organoaluminum compounds useful as activators include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.

The ionizing compound may contain an active proton, or some other cation that associates with the remainder of the ionizing compound but is not coordinated thereto or only weakly coordinated. Such compounds are disclosed in EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP- -0 277 004 and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124, and U.S. Patent Application Serial No. 08 / 285,380, filed August 3, 1994, all of which are incorporated herein by reference in their entirety ). ≪ / RTI >

Other activators include, but are not limited to, tris (2,2 ', 2 " -nonafluorobiphenyl) fluoroaluminates as disclosed in PCT Publication No. WO 98/07515 (the disclosure of which is incorporated herein by reference in greater detail) A combination of activators is also included in the present invention, for example, a combination of an alumoxane and an ionizing activator (see, for example, EP-B1 0 573 120, PCT Publication No. WO 94/07928 And WO 95/14044, and U.S. Pat. Nos. 5,153,157 and 5,453,410, all of which are incorporated herein by reference in their entirety). WO 98/09996, which is incorporated herein by reference, includes perchlorates, peroidates And the activation of bulky ligand metallocene catalyst compounds by iodate. WO 98/30602 and WO 98/30603, incorporated herein by reference, disclose the activation of bulky ligand metallocene catalyst compounds The use of lithium (2,2'-bisphenyl-ditrimethylsilicate) 4THF as a topic is described. The use of an organo-boron-aluminum activator is described in WO 99/18135, incorporated herein by reference EP-B1-0 781 299 describes the use of a silylium salt in combination with a mordant anion in a non-mordant phase. Further, radiation (see EP-B1-0 615 981 incorporated herein by reference) ), Electrochemical oxidation, and the like are also included as activating methods for the purpose of imparting neutral bulky ligand metallocene catalyst compounds or precursors to bulky ligand metallocene cations capable of polymerizing olefins Other activators or methods for activating bulky ligand metallocene catalyst compounds are described, for example, in U.S. Patent Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32 775, WO 99/42467 (dioctadecylmethylammonium-bis (tris (pentafluorophenyl) borane) benzimidazolide).

In one embodiment, the activator is selected from the group consisting of a Lewis acid compound, more preferably an aluminum-based Lewis acid compound, most preferably one or two, preferably at least one, preferably two, halogenated aryl ligands and no halogenated aryl ligands Is a neutral aluminum-basic Lewis acid compound having an additional monoanionic ligand. The Lewis acid compounds in these embodiments are based on aluminum and include at least one bulky electron-withdrawing moiety ligand, such as a halogenated aryl ligand of tris (perfluorophenyl) borane or tris (perfluoronaphthyl) borane These olefin catalyst activator Lewis acids are also included. These bulky ligands are sufficient to allow the Lewis acid to act as an electronically stabilized, non-conjugated satellite anion. Stable ionic complexes may be used where the anion is not a suitable ligand donor for the strong Lewis acidic cationic Group 15-containing transition metal cations used in the insertion polymerization, i. E., A ligand that neutralizes the cations and makes them inert for polymerization Lt; / RTI > Lewis acids meeting the description of this preferred activator may be represented by formula VII:

R _{n is} Al (ArHal) _3-n

Wherein R is a monoanionic ligand and ArHal is a halogenated C ₆ aromatic or higher polycyclic aromatic hydrocarbon or aromatic ring assembly of carbon atoms wherein two or more rings (or fused ring systems) Directly or together, n is 1 to 2, preferably n is 1.

In another embodiment, at least one (ArHal) in formula (VII) is a halogenated C ₉ aromatic or higher, preferably fluorinated naphthyl. Suitable non-limiting R ligands include substituted or unsubstituted C ₁ to C ₃₀ hydrocarbyl aliphatic or aromatic groups wherein substituted is at least one hydrogen on the carbon atom is replaced by a hydrocarbyl, halide, halocarb, hydrocarbyl, Substituted by an organic metalloid, dialkylamido, alkoxy, siloxy, aryloxy, alkylsulfido, arylsulfido, alkylphosphido, alkylphosphido or other anionic substituents; Fluoride; A bulky alkoxide, in which the bulky C ₄ and higher hydrocarbyl groups such as tert-butoxide and 2,6-dimethyl-phenoxide and 2,6-di (tert-butyl) ₂₀ or less); -SR; -NR ₂ and -PR ₂ , wherein each R is independently a substituted or unsubstituted hydrocarbyl as defined above; And C ₁ to C ₃₀ hydrocarbyl substituted organic metalloids such as trimethylsilyl.

Examples of ArHal include the phenyl, naphthyl and anthracenyl radicals of the U.S. Patent No. 5,198,401 when halogenated and the biphenyl radical of WO 97/29845. The term halogenated or halogenated means that in the present application at least one third of the hydrogen atoms on the carbon atoms of the aryl-substituted aromatic ligand are replaced by halogen atoms, more preferably the aromatic ligand is perhalogenated. Fluorine is the most preferred halogen.

In another embodiment, the molar ratio of metal of the activator component to the metal of the supported Group 15-containing catalytic compound is from 0.3: 1 to 1000: 1, preferably from 20: 1 to 800: 1, most preferably from 50: : 1 to 500: 1. In the case where the activating agent is an ionizing activator such as based on anion tetrakis (penta-fluorophenyl) boron, the molar ratio of metal of the activator component to the metal component of the Group 15-containing hafnium catalyst compound is preferably from 0.3: 1 to 3: 1.

The 15 group-containing metal compound and / or the bulky ligand metallocene catalyst compound may be combined with at least one of the catalyst compounds represented by the general formulas (III) to (VI) and the at least one activator, It belongs to the invention.

In another embodiment of the mixed catalyst composition, the modified alumoxane is combined with the first and second metal compounds of the present invention to form a catalyst system. In another embodiment, MMAO3A (modified methyl alumoxane in hexane, available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A; see, for example, U.S. Patent No. 5,041,584, Quot; Aluminoxane ") is combined with the first and second metal compounds to form a catalyst system.

In certain embodiments, when using the metal compounds represented by formulas (1) and (2), both of which are activated by the same activator, the preferred weight percentages are based on the weight of the two metal compounds (excluding activators or optional supports) 10 to 95% by weight of a compound of formula I and 5 to 90% by weight of a compound of formula 2, preferably 50 to 90% by weight of a compound of formula I and 10 to 50% More preferably 60 to 80% by weight of the compound of formula (1) and 40 to 20% by weight of the compound of formula (2). In a particularly preferred embodiment, the compound of formula (2) is activated with methylalumoxane and then combined with the compound of formula (2) before being injected into the reactor.

In certain embodiments, when compound (I) and indenyl zirconium trispivalate (both activated by the same activator) are used, the preferred weight percent based on the weight of both catalysts (excludes activators or optional supports) ) Comprises 10 to 95% by weight of compound (I) and 5 to 90% by weight of indenyl zirconium trispivalate, preferably 50 to 90% by weight of compound (I) and 10 to 50% by weight of indenyl zirconium tris More preferably 60 to 80% by weight of compound (I) and 40 to 20% by weight of indenyl zirconium trispivalate. In a particularly preferred embodiment, the indenyl zirconium trispivalate is activated with methylalumoxane, then compounded with compound (I) and then injected into the reactor.

Generally, the compounded metal compound and the activator are compounded in a ratio of about 1000: 1 to about 0.5: 1. In a preferred embodiment, the metal compound and the activator are compounded in a ratio of about 300: 1 to about 1: 1, preferably about 150: 1 to about 1: 1, and the ratio for borane, borate, aluminate, Is from about 1: 1 to about 10: 1, and the ratio is from about 0.5: 1 to about 10: 1 for alkyl aluminum compounds such as diethyl aluminum chloride combined with water.

A typical type of catalyst system

Alternatively, the mixed catalyst composition of the present invention comprises a Group 15-containing metal compound as described above and a conventional type of transition catalyst.

Typical types of transition metal catalysts are the customary Ziegler-Natta, vanadium and Phillips type catalysts known in the art. Ziegler-Natta catalysts are, for example, those described in Ziegler-Natta Catalysts and Polymerizations, John Boor, Academic Press, New York, 1979. Common types of transition metal catalysts are also discussed in U.S. Patent Nos. 4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741, all of which are incorporated herein by reference in their entirety. Typical types of transition metal catalyst compounds that can be used in the present invention include transition metal compounds of group 3 to 17, preferably groups 4 to 12, and more preferably groups 4 to 6 of the Periodic Table of the Elements.

The conventional type of transition metal catalyst may be represented by the formula of MR _x wherein M is a metal of group 3 to 17, preferably a group 4 to 6, more preferably a group 4 metal, Titanium, R is a halogen or hydrocarbyloxy group, and x is the oxidation state of the metal M. Non-limiting examples of R include alkoxy, phenoxy, bromide, chloride and fluoride. M is a transition metal catalyst of the conventional type of titanium is _{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 Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br, TiCl ₃揃_1/3 AlCl _3, and Ti (OC ₁₂ H ₂₅ ) Cl ₃ .

Common types of transition metal catalyst compounds of magnesium / titanium electron donor complexes useful in the present invention are described, for example, in U.S. Patent Nos. 4,302,565 and 4,302,566, which are incorporated herein by reference in their entirety. A MgTiCl ₆ (ethyl acetate) ₄ derivative is particularly preferred.

British Patent Application No. 2,105,355 and U.S. Patent No. 5,317,036, which are incorporated herein by reference, describe various conventional types of vanadium catalyst compounds. Non-limiting examples of typical types of vanadium catalyst compounds include vanadyltrihalides, alkoxy halides and alkoxides such as VOCl ₃ , VOCl ₂ (OBu) (where Bu is butyl) and VO (OC ₂ H ₅ ) ₃ ; Vanadium tetra-halide and vanadium alkoxy halides such as VCl ₄ and VCl ₃ (OBu); Vanadium and vanadyl acetylacetonate and chloroacetylacetonates such as V (AcAc) ₃ and VOCl ₂ (AcAc) (AcAc is acetylacetonate). Preferred conventional types of vanadium catalyst compounds are VOCl ₃ , VCl ₄ and VOCl ₂ -OR where R is a hydrocarbon radical, preferably a C ₁ to C ₁₀ aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl, isopropyl, butyl, n-butyl, iso-butyl, tert-butyl, hexyl, cyclohexyl, naphthyl and the like) and vanadium acetylacetonate.

Typical types of chromium catalyst compounds (mainly referred to as Phillips-type catalysts) suitable for use in the present invention are CrO ₃ , chromosene, silylchromate, chromyl chloride (CrO ₂ Cl ₂ ), chromium- Chromate, acetylacetonate (Cr (AcAc) ₃ ), and the like. Non-limiting examples are described in U.S. Patent Nos. 3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, the entire disclosures of which are incorporated herein by reference.

Another conventional type of transition metal catalyst compound and catalyst system suitable for use in the present invention are 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, 5,852,144, 5,854,164 And 5,869,585, and European Patent Publication Nos. EP-A2 0 416 815 A2 and EP-A1 0 420 436.

Other catalysts include cationic catalysts such as AlCl ₃ , and other cobalt, iron, nickel, and palladium catalysts known in the art. See, for example, U.S. Patent Nos. 3,487,112, 4,472,559, 4,182,814, and 4,689,437, which are incorporated herein by reference in their entirety.

Typically, the conventional types of transition metal catalyst compounds, except for some conventional types of chromium catalyst compounds, are activated by one or more of the conventional types of cocatalysts described below. In addition, conventional types of transition metal catalysts may be activated using activators known in the art as described herein above.

A common type of promoter compound for the conventional type of transition metal catalyst compound may be represented by the formula M ³ M ⁴ _v X ² _c R ³ _bc where M ³ is a group 1 to 3 group of the Periodic Table of Elements and Group 12 to group 13 elements; M ⁴ is a Group 1 metal of the Periodic Table of Elements; v is 0 to 1; Each X < ² > is any halogen; c is a number from 0 to 3; Each R < ³ > is a monovalent hydrocarbon radical or hydrogen; b is from 1 to 4, and bc is at least one. Other conventional types of organometallic cocatalyst compounds for these conventional types of transition metal catalysts are represented by the formula M ³ R ³ _k wherein M ³ is an ion of Group IA, IIA, IIB, or III metals, such as lithium, sodium, Beryllium, barium, boron, aluminum, zinc, cadmium and gallium; k is 1, 2 or 3 depending on the valence of M ^3, the valence is usually different depending upon the particular Group to which it belongs M ^3; R ³ can be a monovalent hydrocarbon radical.

Non-limiting examples of conventional types of organometallic co-catalyst compounds useful in the conventional type of catalyst compounds include methyllithium, butyllithium, diallylated silver, butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc, tri- Butyl aluminum, diisobutyl ethyl boron, diethyl cadmium, di-n-butyl zinc and tri-n-amyl boron, especially aluminum alkyl such as trihexyl aluminum, triethyl aluminum, trimethyl aluminum and tri- . Other conventional types of co-catalyst compounds include the hydride and mono-organic halides of a Group 2 metal, and hydrides and mono- or di-organic halides of Group 3 and Group 13 metals. Non-limiting examples of such conventional type of promoter compounds include diisobutylaluminum bromide, isobutylboron dichloride, methylmagnesium chloride, ethyl beryllium chloride, ethyl calcium bromide, di-isobutyl aluminum hydride, methyl cadmium hydride, Diethylboron hydride, diethyl boron hydride, hexyl beryllium hydride, dipropyl boron hydride, octyl magnesium hydride, butyl zinc hydride, dichloroboron hydride, di-bromo aluminum hydride and bromocadmium hydride. Conventional types of organometallic cocatalyst compounds are known in the art, and a more detailed discussion of these compounds can be found in U.S. Patent Nos. 3,221,002 and 5,093,415, which are incorporated herein by reference.

Support, carrier and general support technology

Mixed catalyst systems comprising the above-described Group 15-containing catalysts and / or Group 15-containing catalyst compounds and bulky ligand metallocene catalyst compounds, or conventional catalyst compounds, are well known in the art or as described below May be combined with one or more support materials or carriers using one of the support methods. In one embodiment, the Group 15-containing catalysts or mixed catalyst systems of the present invention can be deposited in a supported form, for example, a support or carrier, contacted with, deposited on, bonded to, integrated within, do. In addition, when used as a mixing system, a bulky ligand metallocene catalyst system supported on a carrier separate from the Group 15-containing catalyst, particularly one supported catalyst system, is used in one reactor to produce a high molecular weight component And other supported catalyst systems are used in another reactor to produce low molecular weight components.

The term " support " or " carrier " is used interchangeably and can be any support material, including inorganic or organic support materials, and is preferably a porous support material. Non-limiting examples of inorganic support materials include inorganic oxides and inorganic chlorides. Other carriers include dendritic support materials such as polystyrene, functionalized or cross-linked organic supports such as polystyrene divinylbenzene polyolefin or polymer compounds, or other organic or inorganic support materials, or mixtures thereof.

Preferred carriers are inorganic oxides comprising a 2, 3, 4, 5, 13 or 14 metal oxide. Preferred support materials include silica, alumina, silica-alumina, and mixtures thereof. Other useful supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite (EP-B1 0 511 665), phyllosilicate, zeolite, talc, clay and the like. Also, combinations of these support materials may be used, such as silica-chromium, silica-alumina, silica-titania, and the like. Additional support materials may include the porous acrylic polymers described in EP 0 767 184 B1 incorporated herein by reference.

The carrier, most preferably the inorganic oxide, preferably has a surface area in the range of about 10 to about 100 m 2 / g, a pore volume in the range of about 0.1 to about 4.0 cc / g, and an average particle size in the range of about 5 to about 500 μm . More preferably, the surface area of the support is in the range of about 50 to about 500 m 2 / g, the pore volume is in the range of about 0.5 to about 3.5 cc / g, and the average particle size is in the range of about 10 to about 200 μm. Most preferably, the surface area of the carrier is in the range of about 100 to about 400 m 2 / g, the pore volume is about 0.8 to about 5.0 cc / g, and the average particle size is about 5 to about 100 μm. The average pore size of the carrier of the present invention generally has a pore size in the range of 10 to 1000 angstroms, preferably 50 to about 500 angstroms, and most preferably 75 to about 450 angstroms.

Examples of supporting catalysts of the present invention are disclosed 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, 5,554,704, 5,629,253, 5,639,835, And U.S. Patent Application No. 271,598, filed July 7, 1994, and U.S. Patent Application No. 788,736, filed January 23, 1997, all of which are incorporated herein by reference in their entirety for all purposes. And PCT Publication Nos. WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297 and EP-B1-0 685 494, all of which are hereby incorporated by reference in their entirety.

There are a variety of other techniques in the art to support the polymerization catalyst compounds or mixed catalyst systems of the present invention. For example, a mixed catalyst system comprising a Group 15-containing catalyst compound and / or a bulky ligand metallocene catalyst compound can be prepared by polymeric linkage as described in U.S. Patent Nos. 5,473,202 and 5,770,755, Lt; / RTI >ligand; The Group 15-containing catalytic compounds and / or bulky ligand metallocene catalyst compounds of the present invention can be spray dried as described in U.S. Patent No. 5,648,310, which is incorporated herein by reference in its entirety; The supports used with the Group 15-containing metal catalyst compounds and / or the bulky ligand metallocene catalyst compounds of the present invention are described in EP-A-0 802 203, which is hereby incorporated by reference in its entirety Or at least one substituent or leaving group is selected as described in U.S. Patent No. 5,688,880, which is incorporated herein by reference in its entirety.

In one embodiment, the present invention is directed to a Group 15-containing catalyst system comprising a surface modifier used in the manufacture of a supported catalyst system as described in PCT Publication No. WO 96/11960, And / or a bulky ligand metallocene catalyst compound. The catalyst system of the present invention can be prepared in the presence of an olefin, for example, hexene-1.

In another embodiment, a mixing system comprising a Group 15-containing hafnium catalyst system and a bulky ligand metallocene catalyst compound is disclosed in U.S. Patent Application Serial No. 09 / 113,216, filed July 10, 1998, Carboxylic acid salts such as aluminum mono-, di- and tri-stearate, aluminum octoate, oleate and cyclohexylbutyrate.

Methods for producing supported 15 group-containing catalyst systems and / or bulky ligand metallocene catalyst systems are described in U.S. Patent Application No. 265,533, filed June 24, 1994, and 265,532, June 24, 1994, And PCT Publication Nos. WO 96/00245 and WO 96/00243, all of which are hereby incorporated by reference in their entirety. This method uses a Group 15-containing catalyst compound with or without a bulky ligand metallocene catalyst compound. In this method, the catalyst compound or compounds are slurried in a liquid to form a solution, and a separate solution containing the activator and the liquid is formed. The liquid may be a solvent, which may be a solvent, or other liquid capable of forming a solution or the like with the catalyst compound or compounds of the present invention and / or the activator. In a preferred embodiment, the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene. The catalyst compound or compounds and the activator solution are mixed together and the total volume of the solution of the catalyst compound or compound solution and the activator solution or catalyst compound or compounds and the solution of the activator is added to the porous support in an amount of 4 Fold, more preferably less than 3 times, still more preferably less than 2 times, and the preferred range is in the range of 1.1 to 3.5 times, and most preferably in the range of 1.2 to 3 times.

Methods for measuring the total pore volume of a porous support are well known in the art. A detailed description of one of these methods is given in Volume 1, Experimental Methods in Catalytic Research ( Academic Press, 1968) (see especially pages 67-96). This preferred method uses a classic BET Other methods well known in the art are described in Innes, Total Porosity and Particle Density of Fluid Catalysts by Liquid Titration , Vol. 28, No. 3, Analytical Chemistry 332-334 (1956 3 Month)).

Other methods of supporting the catalyst compounds of the present invention are described in U.S. Patent Application Serial No. 09 / 312,878, filed May 17, 1999, which is hereby incorporated by reference in its entirety.

When a mixed catalyst system is used, the Group 15 catalyst compound of the present invention and the bulky ligand metallocene catalyst compound are used in a weight ratio of 1: 1000 to 1000: 1, preferably 1:99 to 99: 1, To 90:10, more preferably from 20:80 to 80:20, more preferably from 30:70 to 70:30, and even more preferably from 40:60 to 60:40. In one embodiment of the mixing system of the present invention, in particular in the slurry polymerization process, the amount of the Group 15-containing catalyst, expressed in micromoles (μmmol), per gram (g) of the supported supported catalyst (including support materials, Containing compound and the bulky ligand metallocene catalyst compound is about 40 [mu] mmol / g, preferably about 38 [mu] mmol / g.

In another embodiment, especially in the gas phase polymerization process using the mixing system of the present invention, the group 15-containing compound (expressed in micromoles) per gram of the supported catalyst (including support materials, mixed catalyst and activator) And bulky ligand metallocene catalyst compounds is less than 30 [mu] mmol / g, preferably less than 25 [mu] mol / g, more preferably less than 20 [mu] mmol / g.

In another embodiment, the R group, or ligand, in Formula VII may be covalently bonded to a support material, preferably a metal / metaloid oxide or polymeric support. Reacting a Lewis base-bearing support material or substrate with a Lewis acid activator to form a support-bound Lewis acid compound as a supported activator, wherein one R group of R _n Al (ArHal) _3-n is attached to a support material And are jointly combined. For example, where the support material is silica, the Lewis base hydroxyl group of the silica is where this bonding occurs at one of the aluminum coordination sites. Preferably, in these embodiments, the support material is preferably a metal or metaloid oxide having a surface hydroxyl group that exhibits _a pK _a that is equal to or less than that observed for amorphous silica, i. E. Less than about 11 or 11, to be.

Without being bound to any particular theory, it is believed that the covalently bonded anionic activator Lewis acid first bonds to the metal / metalloid of the metal oxide support by forming a coordination complex with the silanol group of, for example, silica (acting as a Lewis base) Is believed to form a bronsted acid structure that is formally bipolar (amphoteric). Thereafter, the protons of the Bronsted acid protonate the R-group of the Lewis acid and remove it, at which time the Lewis acid is covalently bound to the oxygen atom. The substituted R group of the Lewis acid is then R'-O-, where R 'is a suitable support material or substrate, such as a silica or hydroxyl group-containing polymeric support. Any support material containing a surface hydroxyl group is suitable for use in this particular support method. Other support materials include glass beads.

In this embodiment, when the support material is a metal oxide composition, these compositions may additionally contain oxides of other metals such as oxides of Al, K, Mg, Na, Si, Ti and Zr, It should be treated by heat and / or chemical means to remove water and free oxygen. Generally, such treatment is carried out in a vacuum in a heating oven, in a heated fluidized bed, or using a dehydrating agent such as an organosilane, siloxane, alkylaluminum compound, or the like. The level of treatment should be such that residual moisture and oxygen are removed as much as possible but a chemically significant amount of hydroxyl functionality is retained. Thus, calcination at temperatures up to 800 ° C for several hours or until decomposition of the support material can be allowed, and if a higher loading of the supported anionic activator is desired, a lower calcination temperature Is suitable. A load of less than 0.1 mmol to 3.0 mmol activator / g SiO ₂ is generally suitable when the metal oxide is silica, for example by varying the calcination temperature from 200 to 800 ° C. Reference is made to Zhuralev, et al , Langmuir 1987, Vol.3, 316, which describes the correlation between the calcination temperature and time and the hydroxyl content of silica at various surface areas.

The tailoring of the hydroxyl groups available as attachment moieties may also be performed by pretreatment with a chemical dehydrating agent less than the stoichiometric amount prior to addition of the Lewis acid. Preferably these used are rarely used and are reactive with a silanol group (e.g., (CH ₃ ) ₃ SiCl) to minimize interference with the reaction of the combined activating agent with the transition metal catalyst compound, And have a single ligand that is degradable. If a calcination temperature of 400 캜 or less is used, a bi-functional coupling agent (e.g., (CH ₃ ) ₂ SiCl ₂ ) can be used to cap the hydrogen bonded pair of silanol groups present under less severe calcination conditions. For example, the effect of a silane coupling agent on an effective silica polymer filler for the modification of the silanol groups on the catalyst support of the present invention (" Investigation of Quantitative SiOH Determination by Silane Treatment of Disperse Silica ", Gorski, et al ., Journ. of Colloid and Interface Science, Vol. 126, No. 2, Dec. 1988). Similarly, the use of Lewis acids in excess of the stoichiometric amount required for reaction with the transition metal compound serves to neutralize excess silanol groups without significant deleterious effects on catalyst preparation or subsequent polymerization.

The polymeric support is preferably a hydroxyl-functional group-containing polymeric substrate, but the functional groups may be primary alkylamines, secondary alkylamines, etc., where these groups are structurally incorporated into the polymer chain, Lt; RTI ID = 0.0 > Lewis < / RTI > acid to be displaced by the polymer-incorporated functional group. For example, reference is made to the functional group containing polymer of U.S. Patent No. 5,288,677, which is incorporated herein by reference.

Other supports include silica, alumina, silica-alumina, magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolite, talc, clay, silica-chrome, silica-alumina, silica-titania, do.

In another embodiment of the present invention, the olefin (s), preferably C ₂ to C ₃₀ olefin (s) or alpha-olefin (s), preferably ethylene or propylene or combinations thereof, In the presence of a supported Group 15-containing metal catalyst and / or a bulky ligand metallocene catalyst of the present invention. The prepolymerization reaction may be carried out batchwise or continuously in gas phase, solution phase or slurry under conditions comprising elevated pressure. The prepolymerization reaction may be carried out using olefin monomers or blends and / or in the presence of molecular weight modifiers such as hydrogen. Examples of prepolymerization processes are described in detail in U.S. Patent Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578 and EP-B-0 279 863 and PCT Publication WO 97/44371.

Supply of Group 15 metal-containing compounds

In another embodiment, the Group 15-containing metal catalyst compound and activator of the present invention are introduced into a liquid carrier, preferably a slurry or gas phase reactor in solution. The catalyst and activator may be supplied separately or together and may be contacted for a long period of time prior to mixing prior to introduction into the reactor or introduction into the reactor. Preferred liquid carriers include alkanes, preferably pentane, hexane, isopentane, toluene, cyclohexane, isopentane, heptane, octane, isohexane and the like. Particularly preferred liquid carriers include hexane, pentane, isopentane and toluene.

The catalyst system, the metal compound and / or the activator are preferably introduced into the reactor in at least one solution. In one embodiment, a solution of an activated metal compound in an alkane such as pentane, hexane, toluene, isopentane, or the like is introduced into a gas or slurry reactor. In another embodiment, the catalyst system or components may be introduced into the reactor in a suspension or emulsion. In one embodiment, the transition metal compound is contacted with an activator in a solvent such as, for example, modified methylalumoxane just prior to feeding the solution into a gaseous or slurry reactor. In another embodiment, a solution of the metal compound is combined with a solution of the activator, allowed to react for a predetermined period of time, and then introduced into the reactor. In one preferred embodiment, the catalyst and activator prior to introduction into the reactor are placed in the reactor for at least 1 second, preferably 5 minutes or more, more preferably 5 to 60 minutes. The catalyst and the activator are usually present in the solution in a concentration of 0.0001 to 0.200 mol / l, preferably 0.001 to 0.05 mol / l, more preferably 0.005 to 0.025 mol / l. Generally, metal compounds and activators are blended at a ratio of about 1000: 1 to about 0.5: 1. In a preferred embodiment, the metal compound and the activator are combined in a ratio of about 300: 1 to about 1: 1, preferably about 10: 1 to about 1: 1, and the ratio to borane is preferably about 1: 1 to about 10: 1, and the ratio to the alkyl aluminum compound (e.g., diethyl aluminum chloride mixed with water) is preferably from about 0.5: 1 to about 10: 1.

In another embodiment, the catalyst system is preferably comprised of a transition metal compound (catalyst) and / or an activator (co-catalyst) introduced into the reactor in solution. The solution of the metal compound is prepared by selecting the catalyst and dissolving it in any solvent such as alkane, toluene, xylene and the like. The solvent may be purified to remove any toxicity that affects catalytic activity, including any trace amounts of water and / or oxygenated compounds. Purification of the solvent can be accomplished, for example, by using activated alumina and activated and supported copper catalysts. The catalyst is preferably completely dissolved in the solution to form a homogeneous solution. If necessary, both the catalyst and the activator can be dissolved in the same solvent. Once the catalyst is dissolved in the solution, it can be stored until use.

In the polymerization reaction, it is preferable to blend the catalyst with the activator prior to injection into the reactor. Additionally, other solvents and reactants may be added to the catalyst solution (on-line or off-line), to the activator (on-line or off-line), or to the activating catalyst or catalyst.

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

The solution delivery catalyst system of the present invention described above has excellent operability over a wide range of reactor conditions and has a resin grade with a flow index of 0.2 dg / min, a melt index of 3 dg / min and a density of 0.950 g / cc to 0.916 g / cc Respectively. No coagulation and sheeting occurred over 10 days of continuous pilot scale operation in the catalyst system. The present invention also has the advantage that it is scarcely contaminated or not contaminated at all. No sheet, lump or debris was observed during or after the polymerization process. There was no evidence of polymer build-up inside the reactor wall or on the recycle gas line. Also, no increase in pressure drop across the heat exchanger, circulating gas compressor or gas distribution plate occurred during the entire operation.

Solution supply of mixed catalyst systems

In another embodiment, the mixed catalyst system and / or activator (cocatalyst) of the present invention is introduced into a reactor in solution. A solution of the metal compound is prepared by selecting the catalyst and dissolving it in any suitable solution such as alkane, toluene, xylene, and the like. The solvent may first be purified to remove any toxicity that affects the catalytic activity, including any traces of water and / or oxygenated compounds. Purification of the solvent can be accomplished, for example, by using activated alumina and an activated supported copper catalyst. The catalyst is preferably completely dissolved in the solution to form a homogeneous solution. If necessary, both the catalyst and the activator can be dissolved in the same solvent. Once the catalyst is dissolved in the solution, it can be stored indefinitely until use.

In the polymerization reaction, it is preferable to mix the catalyst with the activating agent before injecting into the reactor. Additionally, other solvents and reactants may be added to the catalyst solution (on-line or off-line), to the activator (on-line or off-line), or to the activating catalyst or catalyst. See U.S. Patent Nos. 5,317,036 and 5,693,727, EP-A 0 593 083, and WO 97/46599, all of which are incorporated herein by reference, which describe a solution supply system to a reactor. There are many different configurations in which the catalyst and activator can be mixed.

The catalyst system, metal compound and / or activator (s) may be introduced into the reactor in one or more of the solvents. The metal compounds can be activated independently, sequentially or together. In one embodiment, a solution of two activated metal compounds in an alkane, such as pentane, hexane, toluene, isopentane, and the like, is introduced into the gas phase or slurry phase reactor. In another embodiment, the catalyst system or components may be introduced into the reactor in a suspension or emulsion. In yet another embodiment, the second metal compound is contacted with an activating agent such as modified methyl alumoxane in a solvent just prior to introducing the solution into the vapor, slurry or liquid phase reactor. The solution of the Group 15-containing metal compound is mixed with the solution of the second compound and the activator and then introduced into the reactor.

In the following example, A means a catalyst or mixture of catalysts and B means a different catalyst or mixture of catalysts. The mixture of catalysts in A and B may be the same catalyst in different proportions. It is also noted that additional solvents or inert gases may be added at various locations.

Example 1 : A and B and the activator are mixed off-line and fed to the reactor. Example 1 is schematically shown in Fig.

Example 2 : A and B are mixed off-line. The activator is immediately added and then fed to the reactor. Example 2 is schematically shown in Fig.

Example 3 : Contact A or B with activator and immediately add A or B before (off-line) introduction into the reactor. Example 3 is schematically shown in Fig.

Example 4 : After contacting A or B with the activator (on-line), add A or B immediately before introduction into the reactor. Example 4 is schematically shown in Fig.

Example 5 : A and B are each in off-line contact with the activator. The activator, B and activator are then immediately contacted before introduction into the reactor. Example 5 is schematically shown in Fig.

Example 6 : A and B are immediately contacted with the activator, respectively. Subsequently, A and the activator before introduction into the reactor, and B and the activator are immediately contacted (this is done by adjusting the ratio of A to B, the ratio of activator to A, and the ratio of activator to B independently Which is a desirable configuration). Example 6 is schematically shown in Fig.

Example 7 : In this example, A or B is contacted with an activator (on-line) while the separate solution of A or B is in off-line contact with the activator. Both the stream of A or B and the activator are then immediately contacted before introduction into the reactor. Example 7 is schematically shown in Fig.

Example 8 : A makes on-line contact with B. The activator is then immediately fed to the mixture of A and B. Example 8 is schematically shown in Fig.

Example 9 : A activates with an activator off-line. Then, A and the activator are brought into on-line contact with B. The activator is then immediately fed to the mixture of A and B and activator. Example 9 is schematically shown in Fig.

In any of the above examples, means for generating mixing means and / or a predetermined residence time can be used. For example, mixing blades or screws can be used to mix the components, or a specific length pipe can be used to obtain the required contact or residence time between components. &Quot; On-line " means a material in a pipe, tube or container connected directly or indirectly to the reactor system. &Quot; Off-line " means a material in a pipe, tube or vessel that is not connected to the reactor system.

In another embodiment, the present invention is directed to a process for polymerizing an olefin in a gas phase reactor introduced into a polymerization reactor of two or more catalysts and at least one activator liquid carrier. In a preferred embodiment, the catalyst and activator (s) are mixed in a liquid carrier prior to introduction into the reactor.

In another embodiment, the catalyst is mixed in a liquid carrier and introduced into a channeling mean connected to the reactor, followed by introducing the activator (s) as catalyst at the same time or at different times. In another embodiment, the catalyst is incorporated into the liquid carrier and then the activator (s) is introduced into the liquid carrier.

In another embodiment, the liquid carrier containing the catalyst and activator (s) is placed in a reactor for introducing the liquid carrier into the reactor. In another embodiment, the catalyst and the liquid carrier are introduced into the apparatus prior to introducing the activator into the apparatus.

In another preferred embodiment, a composition comprising a liquid carrier comprises a liquid stream that is flowed or atomized into the reactor.

In another preferred embodiment, one or more catalysts, one or more activators and a liquid carrier are placed in an apparatus for introducing into a reactor, wherein after introducing the first catalyst and activator into the apparatus, additional catalyst (s) .

Polymerization method

The catalyst compositions, catalyst systems, mixed catalyst systems, supported catalyst systems or solution feed catalyst systems of the present invention described above are suitable for use in any polymerization process, including solution, gas or slurry processes or combinations thereof. The polymerization process is preferably a gas phase or slurry process, more preferably a single reactor is used, and most preferably, a single gas phase reactor is used.

In one embodiment, the present invention relates to a polymerization or copolymerization reaction involving the polymerization of one or more monomers having 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms . The present invention relates in particular to a process for the production of ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene- Trimethyl-hexene-1 and cyclic olefins or mixtures thereof. Other monomers may include vinyl monomers, diolefins such as dienes, polyenes, norbornenes, norbornadiene monomers. Preferably, a copolymer of ethylene is prepared, wherein the comonomer has 4 to 15 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, most preferably 4 to 7 carbon atoms, Lt; RTI ID = 0.0 > carbon atoms. ≪ / RTI > In other embodiments, the geminally distributed olefins disclosed in WO 98/37109 can be polymerized or copolymerized using the inventions described herein.

In yet another embodiment, ethylene or propylene is copolymerized with two or more different comonomers to form a terpolymer. Preferred comonomers are mixtures of alpha-olefin monomers having from 4 to 10 carbon atoms, more preferably from 4 to 8 carbon atoms, and optionally one or more diene monomers. Preferred ternary copolymers include mixtures such as ethylene / butene-1 / hexene-1, ethylene / propylene / butene-1, propylene / ethylene / hexene-1, ethylene / propylene / norbornene and the like.

In a particularly preferred embodiment, the invention relates to the polymerization of ethylene and at least one comonomer having 3 to 8 carbon atoms, preferably 4 to 7 carbon atoms. The comonomers are especially butene-1, 4-methylpentene-1, hexene-1 and octene-1, and most preferably hexene-1 and / or butene-1.

Typically, in a gas phase polymerization process, a continuous cycle is used, wherein a portion of the reactor system cycle is heated by heat of polymerization in a reactor in a circulating gas stream (also referred to as a recycle stream or flow medium). This heat is removed from the recycle composition at another part of the cycle by the cooling system outside the reactor. Generally, in a gas fluidized bed process for preparing polymers, a gas stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reaction conditions. The gaseous stream is withdrawn from the fluidised bed and recycled back to the reactor. Similarly, the polymer product is discharged from the reactor and a new monomer is added 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)

The reactor pressure in the gas phase process is in the range of about 10 psig (69 kPa) to about 500 psig (3448 kPa), preferably in the range of about 100 psig (690 kPa) to about 400 psig (2759 kPa) Can range from 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).

The reactor temperature in the gas phase process is in the range of from about 30 ° C to about 120 ° C, preferably in the range of from about 60 ° C to about 115 ° C, more preferably in the range of from about 75 ° C to 110 ° C, Lt; 0 > C to about 110 < 0 > C. Altering the polymerization temperature may also be used as a means for altering the final polymer product properties.

The productivity of the catalyst or catalyst system is affected by the main monomer particle pressure. The mole percent of the preferred main monomer (ethylene or propylene, preferably ethylene) is about 25 to 90 mole percent and the monomer partial pressure is in the range of about 75 psia (517 kPa) to about 300 psia (2069 kPa) It is a conventional condition in the polymerization method. In one embodiment, the ethylene partial pressure is about 220 to 240 psi (1517 to 1653 kPa). In another embodiment, the molar ratio of hexene to ethylene in the reactor is from 0.03: 1 to 0.08: 1.

In another embodiment, the reactors used in the present invention and the method of the present invention are operated at a rate of greater than 500 lb / hr polymer to about 200,000 lb / hr (90,900 kg / hr) polymer, preferably 1000 lb / hr (445 kg / more preferably greater than 10,000 lb / hr (4540 kg / hr), even more preferably greater than 25,000 lb / hr (11,300 kg / hr), even more preferably greater than 35,000 lb / hr (15,900 kg / hr) More preferably greater than 50,000 lb / hr (22,700 kg / hr), and most preferably greater than 100,000 lb / hr (45,500 kg / hr).

Other methods of vaporization included in the process of the present invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818, and 5,677,375, and EP-A 0 794 200, EP 0 802 202 and EP-B 634 421, all of which are hereby incorporated by reference in their entirety.

The slurry polymerization process generally employs a pressure in the range of from about 1 to about 50 atm or greater and a temperature in the range of 0 < 0 > C to about 120 < 0 > C. In slurry polymerization, a suspension of the solid particulate polymer is formed in a liquid polymerization diluent medium in which hydrogen is added with ethylene and a comonomer, and sometimes with a catalyst. The suspension containing the diluent is removed intermittently or continuously from the reactor where the volatile components are separated from the polymer and optionally distilled and then recycled to the reactor. The liquid diluent used in the polymerization medium is typically an alkane, preferably a branched alkane, having from 3 to 7 carbon atoms. The medium used should be liquid under the conditions of the polymerization reaction and be relatively inactive. If a propane medium is used, the process should be performed above the critical temperature and pressure of the reaction diluent. Preferably, a hexane or isobutane medium is used.

In one embodiment, the preferred polymerization technique of the present invention refers to a slurry process that maintains the temperature below the temperature at which the polymer is polymerized, or the polymer becomes a solution. Such techniques are well known in the art and are described, for example, in U.S. Patent No. 3,248,179, which is hereby incorporated by reference in its entirety. In a particulate process, the temperature is preferably in the range of about 185 ((85 캜) to about 230 ℉ (110 캜). Two preferred methods of polymerization for the slurry process are a process using a loop reactor and a process using a plurality of stirred reactors in series or in parallel, or a combination thereof. Non-limiting examples of slurry methods include a continuous loop or stirred tank method. Other examples of slurry processes are also described in U.S. Patent No. 4,613,484, which is incorporated herein by reference in its entirety.

In yet another embodiment, the slurry process is carried out continuously in a loop reactor. A slurry-type catalyst in isobutane, or a dry free-flowing powder, which is itself packed with a circulating slurry of polymer particles growing in a diluent of a monomer and a comonomer containing isobutane, in the presence of a solvent-type catalyst, a suspension catalyst, an emulsion- Periodically inject into the reactor loop. Optionally, hydrogen may be added as a molecular weight modifier. Depending on the desired polymer density, the reactor is maintained at a pressure of about 525 psig to 625 psig (3620 kPa to 4309 kPa) and a temperature in the range of about 140 내지 to about 220 ℉ (about 60 캜 to about 104 캜). The heat of reaction is mostly removed through the loop wall because the shape of the reactor is double-jacketed. Following the slurry, the isobutane diluent and all unreacted monomers and comonomers are sequentially discharged from the reactor at regular intervals or continuously into a heated low pressure flash vessel, a rotary dryer and a nitrogen purge column. The resulting hydrocarbon-free powder is formulated for use in a variety of applications.

In one embodiment, the reactor used in the slurry process of the present invention has a flow rate greater than 2000 lb / hr (907 kg / hr), more preferably greater than 5000 lb / hr (2268 kg / hr) / hr < / RTI > (4540 kg / hr). In yet another embodiment, the slurry reactor used in the process of the present invention is operated at a rate greater than 15,000 lb / hr (6804 kg / hr), preferably greater than 25,000 lb / hr (11,340 kg / hr) Kg / hr) can be produced.

In another embodiment, in the slurry process of the present invention, the total reactor pressure is in the range of 400 psig (2758 kPa) to 800 psig (5516 kPa), preferably 450 psig (3103 kPa) More preferably in the range of 500 psig (3448 kPa) to about 650 psig (4482 kPa), and most preferably in the range of about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In another embodiment, the concentration of ethylene in the reactor liquid medium in the slurry process of the present invention is from about 1 to 10 wt%, preferably from about 2 to about 7 wt%, more preferably from about 2.5 to about 6 wt% Most preferably from about 3 to about 6% by weight.

The preferred method of the present invention, preferably a slurry or gas phase process, is carried out in the absence of a scavenger such as triethylaluminum, trimethylaluminum, triisobutylaluminum and tri-n-hexylaluminum and diethylaluminum chloride, dibutylzinc, Lt; / RTI > Such preferred methods are described in PCT Publication No. WO 96/08520 and U.S. Patent No. 5,712,352, which are incorporated herein by reference in their entirety.

In a preferred embodiment of the invention, a slurry of the mineral distearate in mineral oil is mixed with the first and / or second metal complexes from the metal compound and / or activator, either separately or together, and / Are introduced together into the reactor. More information on the use of aluminum stearate type additives can be found in U.S. Patent No. 09 / 113,261, filed June 10, 1998, which is incorporated herein by reference.

In another embodiment, when the second metal compound and the Group 15 metal compound of the catalyst system are continuously introduced into the reactor, the second metal compound is first added and / or activated, and then the Group 15 metal compound is added ).

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

In embodiments, the mole ratio of comonomer to ethylene, C _x / C ₂ , where 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, more preferably about 0.002 to 0.008 .

The melt index (and other properties)

1) adjusting the amount of the first catalyst in the polymerization system and /

2) adjusting the amount of the second catalyst in the polymerization system and /

3) adding hydrogen to the polymerization process and /

4) varying the amount of liquid and / or gas discharged or removed from the process,

5) varying the amount and / or composition of the regeneration liquid and / or regeneration gas returned from the polymer discharged from the polymerization process by the polymerization process,

6) using a hydrogenation catalyst in the polymerization process and /

7) changing the polymerization temperature and /

8) changing the ethylene partial pressure in the polymerization process and /

9) change the ratio of ethylene to hexene in the polymerization process and /

10) By varying the ratio of activator to transition metal in the activation sequence,

The hydrogen concentration in the polymerization system can be adjusted and varied.

The hydrogen concentration in the reactor is about 100 to 5000 ppm, preferably 200 to 2000 ppm, more preferably 250 to 1900 ppm, still more preferably 300 to 1800 ppm, still more preferably 350 to 1700 ppm, More preferably 500 to 1500 ppm, further preferably 500 to 1200 ppm, further preferably 600 to 1200 ppm, preferably 700 to 1100 ppm, and most preferably, And more preferably 800 to 1000 ppm. The hydrogen concentration in the reactor is inversely proportional to the polymer weight average molecular weight (M _w).

The polymer

The novel polymers produced by the process of the present invention can be used in a wide variety of products and end-use applications. Preferably, the novel polymers include polyethylene, and bimodal polyethylene produced by the mixed catalyst system of the present invention in a single reactor. In addition to bimodal polymers, mixed systems for producing unimodal or multimodal polymers are also within the scope of the present invention.

When the Group 15-containing metal compound is used alone, it is preferable to use a polymer having a high weight average molecular weight Mw (for example, more than 100,000, preferably more than 150,000, preferably more than 200,000, preferably more than 250,000, More than 300,000) are produced. When other metal compounds are used alone, it is preferable to use a low molecular weight polymer (for example, less than 80,000, preferably less than 70,000, preferably less than 60,000, more preferably less than 50,000, more preferably less than 40,000, Is less than 30,000, more preferably more than 5,000 to less than 20,000, more preferably more than 10,000 to less than 20,000).

Polyolefins, particularly polyethylene, produced by this invention has a density (as measured by ASTM 2839) of 0.88 to 0.97 g / cm ^3. Preferably it may be 0.910 to 0.965 g / cm ^3, more preferably the polyethylene has a density of 0.915 to 0.960 g / cm ^3, even more preferably 0.920 to 0.955 g / cm ³ produced. In some embodiments, a density of 0.915 to 0.940 g / cm < ³ > is preferred; in other embodiments, a density of 0.930 to 0.970 g / cm < ³ > is preferred.

In a preferred embodiment, the recovered polyolefin typically has a melt index I ₂ (measured by ASTM D-1238, condition E at 190 캜) of about 0.01 to 1000 dg / min or less. In a preferred embodiment, the polyolefin is an ethylene homopolymer or copolymer. In a preferred embodiment for certain applications, such as films, pipes, molded products, etc., a melt index of 10 dg / min or less is preferred. For some films and molded articles, a melt index of 1 dg / min or less is preferred. Polyethylene having an I ₂ of 0.01 to 10 dg / min is preferred.

In a preferred embodiment, the polymer produced by the present invention has a density of 0.1 to 10 dg / min, preferably 0.2 to 7.5 dg / min, preferably 0.2 dg / min or less, preferably 1.5 dg / min or , preferably less than 1.2 dg / min or less, more preferably 0.5 to 1.0 dg / min, more preferably from 0.6 to 0.8 dg / min or less than the I ₂₁ (ASTM-D-1238- from 190 ℃ F).

In yet another embodiment, the polymer of the present invention has a melt flow index " MIR " (I ₂₁ / I, preferably 80 or more, preferably 90 or more, preferably 100 or more, ₂ ).

In another embodiment, the polymer is I ₂₁ (as measured by ASTM 1238, Condition F at 190 ℃, sometimes called flow index hereinafter) is 2.0 dg / min or less, preferably 1.5 dg / min or less, preferably Advantageously 1.2 dg / min or less, more preferably 0.5 to 1.0 dg / min, more preferably from 0.6 to 0.8 dg / min, I ₂₁ / I ₂ of 80 or higher, preferably 90 or more , Preferably 100 or more, preferably 125 or more, and also has one or more of the following properties:

(a) a Mw / Mn of from 15 to 80, preferably from 20 to 60, preferably from 20 to 40; Molecular weights (Mw and Mn) were determined as described in the Examples section below;

(b) a Mw of 180,000 or more, preferably 200,000 or more, preferably 250,000 or more, preferably 300,000 or more;

(c) 0.94 to 0.970 g / cm ^3, preferably 0.945 to 0.965 g / cm ^3, preferably 0.950 to 0.960 g / cm ³ in density (as measured by ASTM 2839);

(d) a transition metal of 5.0 ppm or less, preferably a transition metal of 2.0 ppm or less, preferably a transition metal of 1.8 ppm or less, preferably a transition metal of 1.6 ppm or less, preferably a transition metal of 1.5 ppm or less, preferably a Group 4 metal 2.0 ppm or less, preferably a Group 4 metal 1.8 ppm or less, preferably a Group 4 metal 1.6 ppm or less, preferably a Group 4 metal 1.5 ppm or less , A residual metal content of less than 2.0 ppm zirconium, preferably less than or equal to 1.8 ppm zirconium, preferably less than or equal to 1.6 ppm zirconium, preferably less than or equal to 1.5 ppm zirconium (Inductively Coupled Plasma Atomic Emission Spectroscopy (ICPAES), where all organic materials are completely decomposed Heating the sample to, the solvents are present (hydrofluoric acid to dissolve, for example, a silica support), another acid to dissolve the substrate, the case that the support and containing nitric acid present);

(e) a weight average molecular weight component as determined by size-exclusion chromatography of 35% by weight or higher, preferably 40% or higher. In a particularly preferred embodiment, the high molecular weight fraction is present in an amount of from 35 to 70% by weight, more preferably from 40 to 60% by weight.

In a preferred embodiment, a polyethylene having a density of 0.94 to 0.970 g / cm ³ (as measured by ASTM D 2839), 0.5 g / 10 min or less I ₂ is prepared using the catalyst composition described above.

In another embodiment, the catalyst composition described above is used to produce a catalyst having a density of I _{21 of} less than 10, a density of about 0.940 to 0.950 g / cm ³ , or a density of I _{21 of} less than 20, a density of less than about 0.945 g / cm ³ Polyethylene is produced.

In another embodiment, the polymer of the present invention is made into a pipe by methods known in the art. For pipe applications, the polymers of the present invention have an I ₂₁ of from about 2 to about 10 dg / min, preferably from about 2 to about 8 dg / min. In yet another embodiment, the pipe of the present invention meets ISO conditions.

In another embodiment, a polyethylene pipe is prepared using the catalyst composition of the present invention and capable of withstanding water to an internal test medium and water or air at ambient temperature for 20 to 50 years at ambient temperature (ISO TR 9080 (Cone stress) as measured by.

In yet another embodiment, the polymer has a notched elongation test (tolerance to slow crack growth) at a pressure of 3.0 MPa over 150 hours, preferably above 3.0 MPa, more preferably above 3.0 MPa for 600 hours (ASTM Measured by -F1473).

In yet another embodiment, a polyethylene pipe having a predicted S-4 T _c for a 110 mm pipe of less than -5 ° C, preferably less than -15 ° C, and more preferably less than -40 ° C, (ISO DIS 13477 / ASTM F1589).

In another embodiment, the polymer has a melt index of greater than about 17 lb / hr per inch (mold circumference), preferably greater than about 20 lb / hr per inch (mold circumference), more preferably greater than about 22 lb / hr per inch (Mold circumference)).

The polyolefin of the present invention can be made of films, molded products (including pipes), sheets, wires and cable coatings and the like. The film may be formed by conventional techniques known in the art, including extrusion, coextrusion, lamination, hollows and casting. The film may be obtained by a flat film or tubular process and then stretched to the same or different extent in the minor axis direction or in two directions perpendicular to each other in the plane of the film. The degree of stretching may be the same or different in both directions. Particularly preferred methods for forming the polymer into a film include extrusion or coextrusion on a blowing or cast film line.

In another embodiment, the polymers of the present invention are made into films by methods known in the art. For film applications, the polymer of the present invention has a viscosity of from about 2 to about 50 dg / min, preferably from about 2 to about 30 dg / min, even more preferably from about 2 to about 20 dg / min, Has an I ₂₁ of from about 5 to about 15 dg / min, and even more preferably from about 5 to about 10 dg / min.

In yet another embodiment, the polymer has an MD tear strength of 5 mil (13 mu m) of from about 5 g / mil to about 25 g / mil, preferably about 15 g / mil to about 25 g / mil, 20 g / mil to 25 g / mil.

The films thus produced can be used in the form of slips, antisettling agents, antioxidants, fillers, antifogging agents, UV stabilizers, antistatic agents, polymer processing aids, neutralizing agents, lubricants, surfactants, pigments, May further contain additives. Preferred additives include silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metal stearates, calcium stearate, zinc stearate, talc, BaSO _4, diatomaceous earth, wax, carbon black, flame retardant, low-molecular weight resin, Hydrocarbon resin, glass beads, and the like. The additives may be present in conventional effective amounts well known in the art, such as from 0.001% to 10% by weight.

In another embodiment, the polymer of the present invention is made into a molded article by methods known in the art, for example, blow molding and injection-stretch molding. For molded articles, the polymers of the present invention have an I ₂₁ of from about 20 dg / min to about 50 dg / min, preferably from about 35 dg / min to about 45 dg / min.

In another embodiment, the polymers of the present invention, including those described above, are produced with a ash content of less than 100 ppm, more preferably less than 75 ppm, and even more preferably less than 50 ppm. In yet another embodiment, the ash contains a negligible amount of titanium as measured by inductively coupled plasma atomic emission spectroscopy (ICPAES) as is well known in the art.

In yet another embodiment, the polymers of the present invention contain nitrogen containing ligands that can be detected by high performance mass spectrometry (HRMS) well known in the art.

SUMMARY OF THE INVENTION

The present invention relates to catalyst compounds, catalyst systems and mixed catalyst systems, and their use in polymerization processes, polymers made therefrom and products made from such polymers.

In one embodiment, the present invention provides a catalyst composition comprising a Group 15-containing metal compound, at least one metal compound of the mixture composition being a Group 15-containing metal compound and the other metal compound being a bulky ligand metallocene compound, Metal catalysts, or combinations thereof, and catalyst systems comprising such catalysts, their use in olefin (s) polymerization and polymers made therefrom.

In another embodiment, the invention relates to compounds of the group 15 to group 2, 3 or 14, preferably groups 3 to 7, more preferably groups 4 to 6, Group IV metal catalyst compound, at least one metal compound is the Group 15-containing catalyst compound, and the other metal compound comprises at least two metal compounds that are bulky ligand metallocene compounds, conventional transition metal catalysts, or combinations thereof. To catalyst systems comprising such catalysts, to their use in olefin (s) polymerization and to polymers made therefrom. In this embodiment, it is preferred that the other metal compound is a bulky ligand metallocene compound.

In another embodiment, the present invention relates to a compound of formula I, wherein at least one of the groups is bonded to at least one leaving group and at least two Group 15 atoms, at least one of which is also bonded to a Group 15 or Group 16 atom through another group of catalyst compounds Group metal atom, one metal compound is the Group 15-containing catalyst compound, the second metal compound is different from the first metal compound, and is a bulky ligand metallocene catalyst, a conventional type of transition metal catalyst, or A combination thereof, a catalyst system comprising said catalyst, their use in olefin (s) polymerization, and a polymer prepared therefrom.

In another embodiment, the present invention provides a method for supporting the catalyst composition, a supported catalyst system itself; And their use in olefin (s) polymerization processes.

In another embodiment, the present invention relates to the use of an Lewis acid aluminum containing activator with the catalyst composition and system.

In another embodiment, the present invention relates to a method of feeding the catalyst composition and system to a polymerization reaction reactor in a liquid carrier.

In yet another embodiment, the present invention relates to a method of polymerizing an olefin (s) using any of the above-mentioned catalyst systems or supported catalyst systems, especially in a gas phase or slurry phase process.

In another embodiment, the present invention relates to a process for polymerizing an olefin (s) using, in particular, the abovementioned mixed catalyst composition in a single polymerization reactor. More preferably, the process utilizes a continuous gas phase single reactor process to produce a multimodal polymer.

In yet another embodiment, the present invention relates to a polymer prepared using the mixed catalyst composition, preferably a novel bimodal MWD HDPE.

The following examples are provided to better understand the invention, including its exemplary advantages.

Justice:

Mn and Mw were determined by gel permeation chromatography on a gel permeation chromatography (GPC) instrument at 150 [deg.] C with a differential refractometer detector. The GPC column was calibrated by operating a standard material with a series of molecular weights, and the molecular weight was calculated using the Mark Houwink coefficient for that polymer.

MWD = Mw / Mn

Density was measured according to ASTM D 1505.

CDBI (Composition Distribution Width Index) was determined according to the method of WO 93/03093, published Feb. 18, 1993, except that the fraction having a molecular weight below Mn 10,000 was ignored in the calculation.

The melt index (MI) I ₂ was measured according to ASTM D-1238, Condition E at 190 占 폚.

I ₂₁ was measured according to ASTM D-1238, Condition F at 190 占 폚.

Melt index ratio (MIR) is the ratio of I ₂₁ to I ₂ as measured by ASTM D-1238.

The weight percent of comonomer was determined by proton NMR.

The dart impact strength was measured according to ASTM D 1709.

MD and TD Elmendorf tear strength was measured according to ASTM D 1922.

The MD and TD 1% Secant coefficients were measured according to ASTM D 882.

MD and TD tensile strengths and maximum tensile strengths were measured according to ASTM D 882.

MD and TD elongation and maximum elongation were measured according to ASTM D 412.

The MD and TD coefficients were measured according to ASTM 882-91.

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

The 45 degree gloss was measured according to ASTM D 2457.

BUR is the blow up rate.

The 26 inch dart impact strength was measured according to ASTM D 1709, Method A.

Escobar alkylene (ESCORENE: trade name) is LL3002.32 Exxon Chemical Company, and (Exxon Chemical Company, Houston, Texas ), a density of 0.918 g / cc, I ₂ is 2 dg / min, available from, CDBI (composition distribution breadth Quot;) is a linear low density ethylene-hexene copolymer prepared in a single gas phase reactor using a Ziegler-Natta catalyst having a <

EXCEED ™ ECD 125 was prepared using a metallocene catalyst having a density of about 0.91 g / cc and an MI of 1.5 dg / 10 min, available from Exxon Chemical Company, Houston, Tex. Linear low density ethylene-hexene copolymer prepared in a gas phase reactor.

The Eskoren (trade name) LL3001.63 was prepared using a Ziegler-Natta catalyst having a density of 0.918 g / cc and an MI of 1.0 g / 10 min, available from Exxon Chemical Company, Houston, Linear low density ethylene-hexene copolymer prepared in the reactor.

The Exceed ™ 350D60 was prepared in a single gas phase reactor using a metallocene catalyst with a density of 0.918 g / cc and an MI of 1.0 g / 10 min, available from Exxon Chemical Company, Houston, Tex. Linear low density ethylene-hexene copolymer.

"PPH" is pounds / hr. " mPPH " is milliPounds / hr. " ppmw " is 1 part by weight per 100 parts by weight. MD is the longitudinal direction. TD is the transverse direction.

EXAMPLES The following examples use a mixed catalyst system comprising a Group 15-containing metal catalyst and a bulky ligand metallocene catalyst.

EXAMPLES Item I. A mixed catalyst system comprising a Group 15-containing metal catalyst and a bulky ligand metallocene catalyst

Preparation of indenyl zirconium trispivalate

A bulky ligand metallocene compound, indenyl zirconium trispivalate, also represented by formula VI, can be prepared by performing the general reaction:

(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

(Wherein Ind is indenyl and Et is ethyl)

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

A 2 L single-armed Schlenk flask was charged with a magnetic stir bar, diethylenetriamine (23.450 g, 0.227 mol), 2-bromo-mesitylene (90.51 g, Bis (diphenylphosphino) -1,1'-binaphthyl (racemic BINAP) (0.455 mol), tris (dibenzylideneacetone) dipalladium (2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol) and toluene (800 ml). The reaction mixture was stirred and heated to 100 < 0 > C. After 18 hours, the reaction was terminated as judged by proton NMR spectroscopy. All other treatments can be performed in air. All solvents were removed in vacuo and the residue was dissolved in diethyl ether (1 liter). The ether was washed with water (3 x 250 ml) and saturated aqueous NaCl solution (180 g in 500 ml) and dried over magnesium sulfate (30 g). The ether was removed in vacuo to give a red oil which was dried at 70 < 0 > C for 12 h under vacuum (yield: 71.10 g, 92%). ^{_{1 H NMR (C 6 D 6}} ) δ6.83 (s, 4), 3.39 (br s, 2), 2.86 (t, 4), 2.49 (t, 4), 2.27 (s, 12), 2.21 (s , 6), 0.68 (br s, 1).

Preparation of Catalyst A (for Example Item I)

1.5% by weight catalyst solution in toluene

Note: All of the following steps were performed in the glove box.

1. 100 g of purified toluene are weighed into a 1 L Erlenmeyer flask with Teflon-coated stir bar.

2. Add 7.28 g of tetrabenzylzirconium.

3. Place the solution in a shaker and stir for 5 minutes. All solids dissolved in solution.

4. Add 5.42 g of ligand I prepared above.

5. Add 551 g of purified toluene and stir the mixture for 15 minutes. No solid remains in solution.

6. Pour the catalyst solution into a labeled 1L clean sample cylinder, take it out of the glove box and place it in a fixed location for operation.

Compound I {[(2,4,6-Me ₃ C ₆ H ₂ ) NCH ₂ CH ₂ ] ₂ NH} Zr (CH ₂ Ph) ₂ Separate recipe

A 500 ml round bottom flask was charged with a magnetic stir bar, tetrabenzylzirconium (Boulder Scientific, Boulder Scientific) (41.729 g, 91.56 mmol) and 300 ml toluene under oxygen free dry nitrogen. The solid ligand I (32.773 g, 96.52 mmol) was added over 1 minute with stirring (the desired compound precipitated). The volume of the slurry was reduced to 100 ml and 300 ml of pentane was added with stirring. The solid yellow-orange product was collected by filtration and dried under vacuum (44.811 g, 80% yield). ^{_{1 H NMR (C 6 D 6}} ) δ7.22-6.81 (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), 2.41 (s, 6), 2.18 (s, 6), 1.89 (s, 2), 0.96 (s, 2).

Preparation of Catalyst B (for Example Item I)

1% by weight of catalyst B solution in hexane

All procedures were carried out in a glove box.

1. Transfer 1 liter of purified hexane to a 1 L Ellen Mayer flask with Teflon-coated stir bar.

2. Add 6.67 g of indenyl zirconium trispivalate dry powder.

3. Place the solution on a magnetic shaker and stir for 15 minutes. All solids dissolved in solution.

4. Pour the solution into a labeled 1L clean sample cylinder, take it out of the glove box, and place it in a stationary position until it is ready for use.

EXAMPLES Item I - Comparative Example 1:

The ethylene-hexene copolymer was prepared in a 14-inch (35.6 cm) medium test factory scale gas-phase reactor operating at 85 ° C and a reactor total pressure of 350 psig (2.4 MPa) with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 40 lb / hr (18.1 kg / hr), hexene was fed to the reactor at a rate of about 0.6 lb / hr (0.27 kg / hr), hydrogen was fed to the reactor at a rate of 5 mPPH . Nitrogen was fed as supplementary gas at about 5 to 8 PPH. The production rate was about 27 PPH. The reactor was equipped with a plenum with a recirculation flow of approximately 1,900 PPH (as described in detail in US Pat. No. 5,693,727, incorporated herein by reference, the plenum was used to make a particle lean zone in a fluidized bed gas phase reactor Lt; / RTI > A tapered catalyst injection nozzle with a hole size of 0.041 inch (0.10 cm) was placed in the plenum air stream. A 1 wt.% Solution of catalyst A in toluene and in-line blend (MMAO-3A, Aluminum 1 wt.%) Were injected in-line before passing through the injection nozzle to the fluidized bed (MMAO-3A is a trademark of Modified Methylalumoxane type 3A Which is a modified methyl alumoxane in heptane available from Akzo Chemicals, Inc.). The MMAO catalyst was adjusted so that the Al: Zr molar ratio was 400: 1. Nitrogen and isopentane were also fed to the injection nozzle as needed to maintain a stable average particle size. A unimodal polymer having nominal 0.28 dg / min (I ₂₁ ) and 0.935 g / cc (density) properties was obtained. Based on the reactor mass balance, the residual zirconium was calculated to be 1.63 ppmw.

Example Item I - Comparative Example 2:

An ethylene-hexene copolymer was prepared in a 14-inch (35.6 cm) medium test factory scale gas-phase reactor operating at 80 ° C and a reactor total pressure of 320 psig (2.2 MPa) with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 37 lb / hr (19.8 kg / hr), hexene was fed to the reactor at a rate of about 0.4 lb / hr (0.18 kg / hr), hydrogen was fed to the reactor at a rate of 12 mPPH . Ethylene was fed to maintain a partial ethylene pressure of 180 psi (1.2 MPa) in the reactor. The production rate was about 25 PPH. The reactor was equipped with a plenum with a recirculation flow of about 1,030 PPH (the plenum was the device used to make the particle lean zone in the fluidized bed gas phase reactor). A tapered catalyst injection nozzle with a hole size of 0.055 inch (0.14 cm) was placed in the plenum air stream. In a 3/16 inch (0.48 cm) stainless steel tube, a 1 wt% catalyst B solution in hexane catalyst was mixed with 0.2 lb / hr (0.09 kg / hr) hexane for about 15 minutes. The mixture of catalyst B and hexene was in-line mixed with cocatalyst (MMAO-3A, 1 wt% aluminum) for about 40 minutes. In addition to the solution, isoprene and nitrogen were added to adjust the particle size. The entire system was passed through the injection nozzle into the fluidized bed. The MMAO to catalyst ratio was adjusted so that the Al: Zr molar ratio was 300: 1. A bimodal polymer having a melt index of 797 g / 10 min was prepared. The density was 0.9678 g / cc. Based on the reactor mass balance, the residual zirconium was calculated to be 0.7 ppmw. SEC analysis and deconvolution using four floury distributions were completed, and the results are shown in Table 1.

Examples Item I - Example 3:

An ethylene-hexene copolymer was prepared in a 14-inch (35.6 cm) medium test factory scale gas-phase reactor operating at 80 ° C and a reactor total pressure of 320 psig (2.2 MPa) with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 53 lb / hr (24 kg / hr), hexene was fed to the reactor at a rate of about 0.5 lb / hr (0.22 kg / hr), hydrogen was fed to the reactor at a rate of 9 mPPH . Ethylene was fed to maintain a partial ethylene pressure of 220 psi (1.52 MPa) in the reactor. The production rate was about 25 PPH. The reactor was equipped with a plenum with a recirculation flow of about 990 PPH (the plenum was the device used to make the particle lean zone in the fluidized bed gas phase reactor). A tapered catalyst injection nozzle with a hole size of 0.055 inches (0.12 cm) was placed in the plenum air stream. In a 3/16 inch (0.48 cm) stainless steel tube, a 1 wt% catalyst B solution in hexane catalyst was mixed with 0.2 lb / hr (0.09 kg / hr) hexane for about 15 minutes. Catalyst B and a mixture of hexene were mixed in-line with cocatalyst (MMAO-3A, 1 wt% aluminum) for about 20 to 25 minutes. A 1 wt% catalyst A solution in toluene in a separate activated stainless steel tube was activated with cocatalyst (MMAO-3A, 1 wt% aluminum) for about 50 to 55 minutes. The two independently activated solutions were combined in a single process line for about 4 minutes. The amount of catalyst A was about 40 to 45 mole% of the total solution supplied. In addition to the solution, isoprene and nitrogen were added to adjust the particle size. The entire system was passed through the injection nozzle into the fluidized bed. The MMAO to catalyst ratio was adjusted so that the Al: Zr molar ratio was 300: 1. A bimodal polymer having a melt index of 0.045 g / 10 min and a flow index of 7.48 g / 10 min was prepared. The density was 0.9496 g / cc. Based on the reactor mass balance, the residual zirconium was calculated to be 1.7 ppmw. SEC analysis and disassembly analysis using four to eight flavor distributions were completed, and the results are shown in Table 1.

Examples Part I - Example 4:

An ethylene-hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operating at 85 < 0 > C and 320 psig (2.2 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 50 lb / hr (about 22.7 kg / hr), some hexene was fed to the reactor at a rate of about 0.7 lb / hr (about 0.32 kg / hr) Lt; / RTI > Ethylene was fed to maintain the ethylene partial pressure in the reactor at 220 psi (1.52 MPa). The production rate was about 29 PPH. The reactor had a plenum with a recycle airflow of about 970 PPH (the plenum is the device used to form the particle lean zone within the fluidized bed gas phase reactor). A tapered catalyst injection opening having a diameter of 0.055 inches (0.14 cm) was placed in the plenum air stream. A solution of 1 wt.% Catalyst B in hexane catalyst was mixed with 0.2 lb / hr (0.09 kg / hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube for about 15 minutes. Catalyst B and the hexene mixture were in-line mixed with cocatalyst (MMAO-3A, 1 wt% aluminum) for about 20-25 minutes. In a separate activated stainless steel tube, 1 wt% catalyst A in toluene solution was activated with a cocatalyst (MMAO-3A, 1 wt% aluminum) for about 50 to 55 minutes. The two independently activated solutions were combined in one process line for about 4 minutes. The amount of catalyst A catalyst was about 40 to 45 mole percent of the total solution fed. In addition to the solution, isopentane and nitrogen were added to adjust the particle size. The entire system was transferred to the fluidized bed through the injection nozzle. The MMAO to catalyst ratio was adjusted so that the Al: Zr molar ratio was 300: 1. A bimodal polymer having a melt index of 0.054 g / 10 min and a flow index of 7.94 g / 10 min was prepared. The density was 0.948 g / cc. 1.1 ppmw of residual zirconium was calculated based on the reactor mass balance. SEC analysis and deconvolution using 7 to 8 Flair distributions were carried out, and the results are shown in Table I below.

EXAMPLES Part I - Example 5:

An ethylene-hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operating at 85 < 0 > C and 320 psig (2.2 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 60 lb / hr (about 27.2 kg / hr), hexene was fed to the reactor at a rate of about 0.8 lb / hr (about 0.36 kg / hr), hydrogen was fed at a rate of 13 mPPH Lt; / RTI > Ethylene was fed to maintain the ethylene partial pressure in the reactor at 220 psi (1.52 MPa). The production rate was about 34 PPH. The reactor had a plenum with a recycle airflow of about 960 PPH (the plenum is the device used to form the particle lean zone in the fluidized bed gas phase reactor). A tapered catalyst injection opening having a diameter of 0.055 inches (0.14 cm) was placed in the plenum air stream. A solution of 1 wt.% Catalyst B in hexane catalyst was mixed with 0.2 lb / hr (0.09 kg / hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube for about 15 minutes. Catalyst B and the hexene mixture were in-line mixed with cocatalyst (MMAO-3A, 1 wt% aluminum) for about 20-25 minutes. In a separate activated stainless steel tube, 1 wt% catalyst A in toluene solution was activated with cocatalyst (MMAO-3A, 1 wt% aluminum) for about 50 to 55 minutes. The two independently activated solutions were combined in one process line for about 4 minutes. The amount of catalyst A catalyst was about 40 to 45 mole percent of the total solution fed. In addition to the solution, isopentane and nitrogen were added to adjust the particle size. The entire system was transferred to the fluidized bed through the injection nozzle. The MMAO to catalyst ratio was adjusted so that the Al: Zr molar ratio was 300: 1. A bimodal polymer having a melt index of 0.077 g / 10 min and a flow index of 12.7 g / 10 min was prepared. The density was 0.9487 g / cc. 0.9 ppmw of residual zirconium was calculated based on the reactor mass balance. SEC analysis and disassembly analysis using 7 to 8 Flair distributions were carried out, and the results are shown in Table I below.

EXAMPLES Part I - Example 6:

An ethylene-hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operating at 85 < 0 > C and 320 psig (2.2 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 60 lb / hr (about 27.2 kg / hr), hexene was fed to the reactor at a rate of about 0.8 lb / hr (about 0.36 kg / hr), hydrogen was fed at a rate of 13 mPPH Lt; / RTI > Ethylene was fed to maintain the ethylene partial pressure in the reactor at 220 psi (1.52 MPa). The production rate was about 34 PPH. The reactor had a plenum with a recycle airflow of about 1,100 PPH (the plenum is the device used to form the particle lean zone in the fluidized bed gas phase reactor). A tapered catalyst injection opening having a diameter of 0.055 inches (0.14 cm) was placed in the plenum air stream. A solution of 1 wt.% Catalyst B in hexane catalyst was mixed with 0.2 lb / hr (0.09 kg / hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube for about 15 minutes. Catalyst B and the hexene mixture were in-line mixed with cocatalyst (MMAO-3A, 1 wt% aluminum) for about 10-15 minutes. 1 wt% catalyst A in toluene solution was added to the activated catalyst B solution for about 5 minutes before spraying into the reactor. The amount of catalyst A catalyst was about 40 to 45 mole percent of the total solution fed. In addition to the solution, isopentane and nitrogen were added to adjust the particle size. The entire system was transferred to the fluidized bed through the injection nozzle. The MMAO to catalyst ratio was adjusted so that the Al: Zr molar ratio was 300: 1. A bimodal polymer having a melt index of 0.136 g / 10 min and a flow index of 38.1 g / 10 min was prepared. The density was 0.9488 g / cc. 0.5 ppmw of residual zirconium was calculated based on the reactor mass balance. SEC analysis and disassembly analysis using 7 to 8 Flair distributions were carried out, and the results are shown in Table I below.

EXAMPLES Part I - Example 7:

The ethylene-hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operated at 85 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 42 lb / hr (about 19.1 kg / hr), hexene was fed to the reactor at a rate of about 0.8 lb / hr (about 0.36 kg / hr), hydrogen was fed at a rate of 13 mPPH Lt; / RTI > Ethylene was fed to maintain the ethylene partial pressure in the reactor at 220 psi (1.52 MPa). The production rate was about 32 PPH. The reactor had a plenum with a recycle airflow of about 2010 PPH (the plenum is the device used to form the particle lean zone within the fluidized bed gas phase reactor). A tapered catalyst injection opening having a diameter of 0.055 inches (0.14 cm) was placed in the plenum air stream. A solution of 0.25 wt% catalyst B in hexane catalyst was mixed with 0.1 lb / hr (0.05 kg / hr) hexene in a 3/16 inch (0.48 cm) stainless steel tube. Catalyst B and the hexene mixture were in-line mixed with cocatalyst (MMAO-3A, 1 wt% aluminum) for about 15 minutes. 0.5% by weight catalyst A in a toluene solution was added to the activated catalyst B solution for about 15 minutes before spraying into the reactor. The amount of catalyst A catalyst was about 65 to 70 mole% of the total solution fed. In addition to the solution, isopentane and nitrogen were added to adjust the particle size. The entire system was transferred to the fluidized bed through the injection nozzle. The MMAO to catalyst ratio was adjusted so that the Al: Zr molar ratio was 500. A bimodal polymer having a melt index of 0.06 g / lOmin and a flow index of 6.26 g / lOmin was prepared. The density was 0.9501 g / cc. 0.65 ppmw of residual zirconium was calculated based on the reactor mass balance. SEC analysis and disassembly analysis using 7 to 8 Flair distributions were carried out, and the results are shown in Table I below.

Sections I-Comparative Examples 1 and 2 provide experimental data on how a single component catalyst system works. Examples 3 and 4 show the effect of temperature on substantially the same reactor conditions and catalyst feed system. The higher the temperature, the lower the M _w / M _{n and} the lower the MFR. Examples 5 and 6 compare the effect of activation design on substantially the same reactor conditions and catalyst feed system. It should be noted that, in Example 6, the overall activity of the catalyst was better. However, the yield of high molecular weight materials was less. Examples 6 and 7 show the ability to regulate the production of high molecular weight materials under substantially the same reactor conditions. Example 7 provided a higher percentage of catalyst A, so higher Mw materials were produced in higher amounts.

EXAMPLES Part I - Example 8:

159 kg (350 pounds) of polyethylene prepared according to Example 4 (referred to as Polymer A) were dissolved in a 1000 ppm Irganox (< RTI ID = 0.0 > ) 1076 and 1500 ppm Agarose (Irgafos < (R) >) 1068 and formed into pellets. The pellets were blown onto a 0.5 mil (13 mu m) membrane on an Alpine blowing membrane extrusion line. Extrusion conditions were: die-160 mm triplex, 1.5 mm die blank, 400 占 폚 die temperature, 48 inch (122 cm) layflat width, target melt temperature 410 占 ((210 占 폚), and an extrusion rate of 310 lb / hr (144 kg / hr), 420 lb / hr (191 kg / hr) and 460 lb / hr (209 kg / hr). The ESCORENE HD 7755.10 (a conventional reactor product series from Exxon Chemical Company, Texas, USA) was run under the same conditions for comparison. All membranes were conditioned at 23 [deg.] C, 50% humidity For 40 hours. Data are reported in Table IA below.

MD is the longitudinal direction, TD is the transverse direction, UT Str is the maximum tensile strength, and U. Elong is the maximum elongation.

Escolen HD 7755.10 is an Exxon Chemical Company polyethylene polymer of Houston, Tex., Having an I ₂₁ of 7.5, an MIR of 125, an Mw of 180,000 and a density of 0.95 g / cc, prepared using a dual reactor system.

Examples Section I - Example 9:

A granular sample of several drums (made with a molar catalyst ratio of 2.3 (Catalyst A / Catalyst B) according to the polymerization procedure described above) was mixed with 1000 ppm of Agarox (trade name) 1076, 10681500 ppm of Agarose (trade name) 1500 ppm. This conductive mixed granular resin was pelletized on a 2 1/2 "(6.35 cm) Prodex mixing line at 400 ° F. The pellets thus prepared were extruded in a 50 mm shortened (18: 1 L / D ratio) and a 100 mm annular die with 1 mm die spacing. The extrusion conditions were 400 [deg.] F (204 [deg.] C) die temperature, 100 lb / hr (46 kg / Typical set temperature profile is 380 ° F / 400 ° F / 400 ° F / 400 ° F / 400 ° F / 400 ° C for barrel 1 / barrel 2 / block adapter / base adapter / vertical adapter / die base / 204 ° C / 204 ° C / 204 ° C / 204 ° C / 210 ° C / 210 ° C) The pellet samples were extruded to give a line speed of 92 fpm (48 cm / sec) A 1.0 mil (25 mu m) film sample was prepared and a 0.5 mil (13 mu m) film sample was prepared with a blow-up ratio (BUR) of 4.0 at a line speed of 94 cm / sec (184 fpm) In all, the bubbles exhibited excellent stability in the form of a " necked-in " wine cup. FLH (frost line height) of the blown bubbles was 1.0 mil (25 mu m) and 0.5 mil (12.5 mu m) (91.4 cm) and 40 inches (101.6 cm) with respect to the extrusion head pressure and motor load. The extrusion head pressure and motor load were measured under the same extrusion conditions using Eskorene (TM) HD 7755.10 (Exxon Chemical Company, Mount Bellevue, Tex. The resulting membrane properties are listed in the following Table IB.All membrane samples were left for 40 hours at 23 ° C and 50% humidity.Dart impact of 0.5 mil (12.5 μm) membrane The strength was 380 g, which exceeded the dart impact strength of Eskorene (TM) HD 7755.10, which showed 330 g.

Examples Section I - Example 10:

A polymer C prepared with a catalyst molar ratio of catalyst A to catalyst B of 0.732 according to the above polymerization procedure and a polymer D made with catalyst molar ratio of catalyst A to catalyst B of 2.6 according to the polymerization procedure, Was conducted by conduction mixing with 1000 ppm of Agarox (trade name) 1076, 1500 ppm of calcium stearate and 1500 ppm of Agarose 1068, and then pelletized and extruded as described in Example 9. All membranes were allowed to stand at 23 < 0 > C, 50% humidity for 40 hours. The dart impact strength of the 0.5 mil (12.5 m) film from both Polymer C and Polymer D was 380 g, which exceeded the dart impact strength of Eskorene (TM) HD 7755.10, which showed 330 g. Data are shown in Table IC below.

Alpine line, 2 "axis, 4 inch (10.2 cm) die, 40 mil (1016 μm) die blank, 410 ° F (210 ° C) die set temperature.

In addition to the above examples, other modifications to the polymerization using the catalyst systems described herein include:

1. Compound I is dissolved in a solvent, preferably toluene, to form the desired weight% solution and then used in combination with other catalyst systems.

2. Catalyst A can be used as a 0.50 wt% solution in toluene and Catalyst B can be used as a 0.25 wt% solution in hexane where the two catalysts are separately activated and then mixed together (parallel activity) The ratio of B to A is about 0.7, or the ratio of B to A (in series activity) is 2.2 to 1.5 when B is added after A is activated.

3. Increase or decrease the Mw / Mn respectively by increasing or decreasing the reaction temperature.

4. Changes in retention time affect product properties. Large changes can have a significant effect. A residence time of from 1 to 5, preferably 4 hours, appears to produce good product properties.

5. Spray the catalyst into the reactor to form a particulate lean zone. The particle lean zone can be formed by flowing the circulating gas through a 6 inch tube at 50,000 lb / hr.

6. The activator, preferably MMAO 3A, can be used as a 7 wt.% Al in isopentane, hexane or heptane at a feed ratio sufficient to produce an Al / Zr ratio of 100 to 300.

7. After the catalyst A is mixed on-line with MMAO 3A, the catalyst B is added on-line and the mixture is injected into the reactor.

7. The catalyst A is mixed on-line with MMAO 3A, the catalyst B is mixed on-line with MMAO 3A, the two catalysts are mixed on-line and then introduced into the reactor.

EXAMPLES OF THE FOLLOWING EXAMPLES Section II utilized a catalyst system comprising a Group 15-containing metal catalyst having a benzyl leaving group.

Examples Section II. A catalyst system comprising a Group 15-containing metal catalyst having a benzyl leaving group

[(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).

{[(2,4,6-Me ₃ C ₆ H ₂ ) NCH ₂ CH ₂ ] ₂ NH} ZrCl ₂ Or (ZrCl ₂ -HN3)

5.480 g of Zr (NMe ₂ ) ₄ (20.48 mmol) was dissolved in 50 mL of pentane in a 250 mL round bottom flask. 6.656 g of [(2,4,6-Me ₃ C ₆ H ₂ ) NHCH ₂ CH ₂ ] ₂ NH (20.48 mmol) was added as a pentane solution (50 mL), and the solution was stirred for 2 hours. The mixed amide {[(2,4,6-Me ₃ C ₆ H ₂ ) NCH ₂ CH ₂ ] ₂ NH} Zr (NMe ₂ ) ₂ was proved by proton NMR but was not isolated. ^{_{1 H NMR (C 6 D 6}} ) δ6.94 (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 residue was dissolved in toluene and was added to the ClSiMe ₃ (55 mmol) 6.0 g at a time. The solution was stirred for 24 hours. The solvent was removed in vacuo and the solid suspended in pentane. The solid was collected by filtration and washed with pentane (5.528 g, 54% yield). The dichloride _{{[(2,4,6-Me 3 C} 6 H 2) NCH 2 CH 2] 2 NH} ZrCl 2 was verified by proton NMR. ^{_{1 H NMR (C 6 D 6}} ) δ6.88 (s, 2), 6.81 (s, 2), 3.32 (m, 2), 2.86 (m, 2), 2.49 (s, 6), 2.47 (m, 4), 2.39 (s, 6), 2.12 (s, 6) and NH were unclear.

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

2.051 g of MAO (6.836 g of a 30% by weight solution in toluene, available from Albemarle Corporation, Bartonough, Louisiana) in a 100 mL round bottom flask and 7.285 g of ZrCl ₂ -HN 30.145 g Was added. The solution was stirred for 15 minutes. 5.070 g of silica (DABISON 948 calcined at 600 DEG C, available from WR Grace, Davison Division, Baltimore, Md.) Was added and mixed. The mixture was vacuum dried overnight to yield 7.011 g of a finished catalyst with a zirconium loading of 0.36% by weight and an Al / Zr ratio of 122: 1.

Preparation of catalyst B (for the purposes of this example section II)

0.801 g of MAO (2.670 g of a 30 wt% solution in toluene, available from Albemalle Corporation, Bartonough, Louisiana) and 4.679 g of toluene in a 100 mL round bottom flask were added with 0.70 g of Zr-HN30. The solution was stirred for 15 minutes. 2.130 g of silica (Davison 948 calcined at 600 占 폚, commercially available from W. R. Grace, Davison Division, Baltimore, Md.) Was added and mixed. The mixture was vacuum dried overnight to yield 2.899 g of a finished catalyst with a zirconium loading of 0.35% by weight and an Al / Zr ratio of 120: 1.

Example Division II - Comparative Example 1

Ethylene polymerization in slurry using Catalyst A

Polymerization was carried out in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, a diaphragm inlet and an outlet line and controlled supply of dry nitrogen and ethylene. The reactor was dried at < RTI ID = 0.0 > 160 C < / RTI > Isobutane (400 mL) was added as a diluent and 0.7 mL of a 25 wt% solution of trioctylaluminum in hexane was added as a scavenger using a gas shutoff syringe. The reactor was heated to 90 < 0 > C. Closed catalyst A 0.200 g was added with ethylene pressure and the reactor was pressurized with 143 psi of ethylene (986 kPa). Polymerization was continued for 40 minutes while maintaining the reactor at 90 < 0 > C and a constant ethylene flow of 143 psi (986 kPa). The reaction was quenched by rapid cooling and evacuated. 10.5 g of polyethylene were obtained (flow index (FI) = no flow, activity = 209 g polyethylene / mmol catalyst · atm · h).

Example Sections II - Example 2

Ethylene polymerization in slurry phase using catalyst B

Polymerization was carried out in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, a diaphragm inlet and an outlet line and controlled supply of dry nitrogen and ethylene. The reactor was dried at < RTI ID = 0.0 > 160 C < / RTI > Isobutane (400 mL) was added as a diluent and 0.7 mL of a 25 wt% solution of trioctylaluminum in hexane was added as a scavenger using a gas shutoff syringe. The reactor was heated to 90 < 0 > C. Closed catalyst B 0.100 g was added with ethylene pressure and the reactor was pressurized with 144 psi of ethylene (993 kPa). Polymerization was continued for 30 minutes while maintaining the reactor at 90 < 0 > C and a constant ethylene flow of 144 psi (993 kPa). The reaction was quenched by rapid cooling and evacuated. 11.8 g of polyethylene were obtained (FI = no flow, activity = 641 g polyethylene / mmol catalyst · atm · h).

From the data presented above it can be seen that the Group 15-containing metal catalyst compounds of the present invention having alkyl substituted with hydrocarbon substituents, preferably aryl groups, under similar conditions have much higher productivity than the same compounds with halogens have.

EXAMPLES OF THE FOLLOWING EXAMPLES Section III utilizes a catalyst system comprising a silica bound aluminum activator.

Examples Section III.

Catalyst systems comprising silica-bound aluminum

_{[(2,4,6-Me 3 C 6} H 2) NHCH 2 CH 2] 2 NH ( Ligand), and the _{{[(2,4,6-Me 3 C} 6 H 2) NCH 2 CH 2] 2 NH } Zr (CH ₂ Ph) ₂ (Zr-HN 3) was prepared as described in Example I part.

Silica-bonded aluminum (Si-O-Al (C ₆ F ₅ ) ₂ )

A sample of 40.686 grams of silica in a 500 mL round bottom flask (available from Davison Division, Darbyhead 948 calcined at 600 DEG C, WR Grace, Baltimore, Md.) Was slurried in 300 mL of toluene. Addition of solid _{Al (C 6 F 5) 3} · toluene (15.470 g, 24.90 mmol) and the mixture was stirred for 30 minutes. The mixture was left for 18 hours. The silica-bound aluminum was isolated by filtration and vacuum-dried for 6 hours to give 49.211 g. Al (C ₆ F ₅ ) ₃ · toluene was prepared according to the method described in EP 0 694 548 A1, which is incorporated herein by reference in its entirety.

Preparation of catalyst A (for the purposes of this example part III)

Zr-HN3 (0.076 g, 0.124 mmol) in 5 mL of toluene was added to 1.000 g of silica-bound aluminum (from Example 4 above) in 20 mL of toluene. The mixture was stirred for 30 minutes. The silica changed from colorless to orange-red. The silica was isolated by filtration and vacuum dried for 6 hours to give 1.051 g. The final transition metal loading for the silica-bound aluminum was 116 μmol / g.

Example Sections III - Example 1

Ethylene-hexene polymerization in slurry phase using catalyst A

Polymerization was carried out in a 1-liter autoclave reactor equipped with a mechanical stirrer, an external water jacket for temperature control, a diaphragm inlet and an outlet line and controlled supply of dry nitrogen and ethylene. The reactor was dried at < RTI ID = 0.0 > 160 C < / RTI > Isobutane (400 mL) was added as a diluent, and 35 mL of 1-hexene and 0.7 mL of 25 wt% trioctylaluminum in hexane were added using a gas shutoff syringe as a scavenger. The reactor was heated to 60 < 0 > C. Closed catalyst A 0.100 g was added with ethylene pressure and the reactor was pressurized with 78 psi ethylene (538 kPa). The polymerization was continued for 30 minutes while maintaining the reactor at 60 < 0 > C and a constant ethylene flow of 78 psi (538 kPa). The reaction was quenched by rapid cooling and evacuated. (Flow index (FI) = no flow, activity = 2320 g polyethylene / mmol catalyst · atm · h, 1-hexene 10.5% by weight incorporation).

EXAMPLES OF THE FOLLOWING EXAMPLES Section IV utilized a solution feed of a Group 15-containing metal catalyst.

Examples Sector IV

Supply of a Group 15-containing metal catalyst solution

_{[(2,4,6-Me 3 C 6} H 2) NHCH 2 CH 2] 2 (NH ligand or pre-Compound I) and _{[(2,4,6-Me 3 C 6} H 2) NCH 2 CH 2 ] ₂ NH} Zr (CH ₂ Ph) ₂ (Compound I) was prepared as described in Example I part.

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

(1.5% by weight in toluene)

Note: All the following procedures were performed in the glove box.

1. 100 g of purified toluene was weighed into an Erlenmeyer flask equipped with a 1 L Teflon coated stir bar.

2. Add 7.28 g of tetrabenzylzirconium.

3. The solution was placed on a stirrer and stirred for 5 minutes. All solids dissolved in the solution.

4. Compound (I) (5.42 g) was added.

5. Add 551 g of additional purified toluene and stir the mixture for 15 minutes. No solids remained in the solution.

6. The catalyst solution was poured into clean, purged 1-L Whitey sample syringes, labeled, removed from the glove box, and placed in the holding area for operation.

Example Sections IV - Example 1

An ethylene hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operated at 85 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 40 lb / hr (about 18 kg / hr), hexene was fed to the reactor at a rate of about 0.6 lb / hr (0.3 kg / hr), hydrogen was fed at a rate of 5 mPPH Lt; / RTI > Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 27 PPH. The reactor had a plenum with a recycle airflow of about 1,900 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection hole having a tapered diameter of 0.041 inch (0.11 cm) was placed in the plenum air stream. A solution of 1 wt% catalyst A in toluene and a cocatalyst [MMAO-3A, 1 wt% aluminum in hexane (MMAO-3A is available commercially from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A Heptane, modified by methyl alumoxane, protected by U.S. Patent No. 5,041,584) was in-line mixed and then transferred to the fluidized bed through the injection port. The MMAO and catalyst were adjusted so that the Al: Zr molar ratio was 400: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. A nomodelly polymer having nominal 0.28 dg / min (I ₂₁ ) and 0.935 g / cc characteristics was obtained. 1.63 ppmw of residual zirconium was calculated based on the reactor mass balance.

Examples Section IV - Example 2:

An ethylene hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operated at 85 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 40 lb / hr (about 18 kg / hr), hexene was fed to the reactor at a rate of about 3.5 lb / hr (about 1.6 kg / hr), hydrogen was fed at a rate of 25 mPPH Lt; / RTI > Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 20 PPH. The reactor had a plenum with a recycle airflow of about 1,900 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection hole having a tapered diameter of 0.041 inch (0.11 cm) was placed in the plenum air stream. A solution of 1 wt% catalyst A in toluene, 0.22 PPH of 1-hexene and cocatalyst (MMAO-3A, 4 wt% aluminum in isopentane) was in-line mixed and then transferred to the fluidized bed through the injection opening. The MMAO and catalyst were adjusted so that the Al: Zr molar ratio was 746: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. A nomodal polymer having nominal 1.2 dg / min (I ₂ ), 29.7 dg / min (I ₂₁ ), 23.9 I ₂₁ / I ₂ ratio and 0.9165 g / cc characteristics was obtained. 0.89 ppmw of residual zirconium was calculated based on the reactor mass balance.

Examples Section IV - Example 3:

An ethylene hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operated at 105 ° C and 350 psig (2.4 MPa) total reactor pressure and with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 40 lb / hr (about 18 kg / hr), hexene was fed to the reactor at a rate of about 0.6 lb / hr (about 0.3 kg / hr), hydrogen was fed at a rate of 6 mPPH Lt; / RTI > Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 24 PPH. The reactor had a plenum with a recycle airflow of about 1,600 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A tapered catalyst injection opening having a diameter of 0.055 inches (0.14 cm) was placed in the plenum air stream. A solution of 1.5 wt.% Catalyst A in toluene and cocatalyst (MMAO-3A, 1.8 wt% aluminum in 25% heptane / 75% hexane solution) were in-line mixed and then transferred to the fluidized bed through the injection opening. MMAO and the catalyst were adjusted so that the Al: Zr molar ratio was 320: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. A Unimodal polymer with nominal 0.67 dg / min (I ₂₁ ) and 0.9358 g / cc characteristics was obtained. 2.33 ppmw of residual zirconium was calculated based on the reactor mass balance.

Examples Section IV - Example 4:

An ethylene hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operated at 85 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 36 lb / hr (about 16.3 kg / hr), hexene was fed to the reactor at a rate of about 3.5 lb / hr (about 1.6 kg / hr), hydrogen was fed at a rate of 28 mPPH Lt; / RTI > Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 18 PPH. The reactor had a plenum with a recycle airflow of about 1,900 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection hole having a tapered diameter of 0.041 inch (0.11 cm) was placed in the plenum air stream. A solution of 1 wt% catalyst A in toluene, 0.22 PPH of 1-hexene and cocatalyst (MMAO-3A, 4 wt% aluminum in isopentane) was in-line mixed and then transferred to the fluidized bed through the injection opening. The MMAO and catalyst were adjusted so that the Al: Zr molar ratio was 925: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. A nomodelly polymer having nominal 1.7 dg / min (I ₂ ), 41.7 dg / min (I ₂₁ ), 24.1 I ₂₁ / I ₂ and 0.917 g / cc characteristics was obtained. 0.94 ppmw of residual zirconium was calculated based on the reactor mass balance.

Examples Section IV - Example 5:

An ethylene hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operated at 85 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 40 lb / hr (about 18 kg / hr), hexene was fed to the reactor at a rate of about 0.6 lb / hr (about 0.3 kg / hr), hydrogen was fed at a rate of 3.5 mPPH Lt; / RTI > Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 22 PPH. The reactor had a plenum with a recycle airflow of about 1,500 PPH (plenum is a device used to form a particle lean zone within a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection hole having a tapered diameter of 0.041 inch (0.11 cm) was placed in the plenum air stream. A solution of 1 wt.% Catalyst A in toluene and cocatalyst (MMAO-3A, 1 wt.% Aluminum in hexane) were in-line mixed and then transferred to the fluidized bed through the injection opening. MMAO and the catalyst were adjusted so that the Al: Zr molar ratio was 450: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. A nomodelly polymer having nominal 0.10 dg / min (I ₂₁ ) and 0.931 g / cc characteristics was obtained. 1.36 ppmw of residual zirconium was calculated based on the reactor mass balance.

Examples Section IV - Example 6:

An ethylene hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operated at 85 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 40 lb / hr (about 18 kg / hr), hexene was fed to the reactor at a rate of about 0.5 lb / hr (about 0.23 kg / hr), hydrogen was fed at a rate of 4 mPPH Lt; / RTI > Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 20 PPH. The reactor had a plenum with a recycle airflow of about 2,050 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection hole having a tapered diameter of 0.041 inch (0.11 cm) was placed in the plenum air stream. A solution of 1 wt% catalyst A in toluene and a cocatalyst (MMAO-3A, 4 wt% aluminum in isopentane) were in-line blended and then transferred to the fluidized bed through the injection opening. MMAO and the catalyst were adjusted so that the Al: Zr molar ratio was 1550: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. A Unimodal polymer having nominal 0.36 dg / min (I ₂₁ ) and 0.943 g / cc characteristics was obtained. 2.5 ppmw of residual zirconium was calculated based on the reactor mass balance.

Examples Sections IV - Example 7:

An ethylene hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operated at 85 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 40 lb / hr (about 18 kg / hr), hexene was fed to the reactor at a rate of about 0.6 lb / hr (about 0.3 kg / hr), hydrogen was fed at a rate of 12 mPPH Lt; / RTI > Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 20 PPH. The reactor had a plenum with a recycle airflow of about 2,050 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection hole having a tapered diameter of 0.041 inch (0.11 cm) was placed in the plenum air stream. A solution of 1 wt% catalyst A in toluene and a cocatalyst (MMAO-3A, 4 wt% aluminum in isopentane) were in-line blended and then transferred to the fluidized bed through the injection opening. The MMAO and catalyst were adjusted so that the Al: Zr molar ratio was 868: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. A Unimodal polymer having nominal 3.5 dg / min (I ₂₁ ), 0.115 dg / min (I ₂ ), 30.2 I ₂₁ / I ₂ ratio and 0.949 g / cc characteristics was obtained. 2.5 ppmw of residual zirconium was calculated based on the reactor mass balance.

Examples Section IV - Example 8:

An ethylene hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operated at 85 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 40 lb / hr (about 18 kg / hr), hexene was fed to the reactor at a rate of about 1.1 lb / hr, and hydrogen was fed to the reactor at a rate of 12 mPPH. Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 25 PPH. The reactor had a plenum with a recycle airflow of about 1,900 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection opening having a tapered opening of 0.041 inches (0.11 cm) was placed in the plenum air stream. A solution of 1 wt% catalyst A in toluene and a cocatalyst (MMAO-3A, 4 wt% aluminum in isopentane) were in-line blended and then transferred to the fluidized bed through the injection opening. MMAO and catalyst were adjusted so that the Al: Zr molar ratio was 842: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. A Unimodal polymer having nominal 41.2 dg / min (I ₂₁ ), 1.22 dg / min (I ₂ ), 33.8 I ₂₁ / I ₂ ratio and 0.940 g / cc characteristics was obtained. 2.77 ppmw of residual zirconium was calculated based on the mass balance of the reactor.

Examples Sections IV - Example 9:

An ethylene hexene copolymer was prepared in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operated at 90 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 48 lb / hr, and hexene was fed to the reactor at a rate of about 0.6 lb / hr (about 0.3 kg / hr) and hydrogen was fed to the reactor at a rate of 10 mPPH. Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 23 PPH. The reactor had a plenum with a recycle airflow of about 1,600 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection nozzle having a tapered diameter of 0.055 inch (1.4 cm) was placed in the plenum air stream. A solution of 1.5 wt% catalyst A in toluene and cocatalyst (MMAO-3A, 1.8 wt% aluminum in 25% heptane / 75% hexane) were mixed in-line and then transferred to the fluidized bed through the injection opening. The MMAO and catalyst were adjusted so that the Al: Zr molar ratio was 265: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. A Unimodal polymer having nominal 0.3 dg / min (I ₂₁ ) and 0.933 g / cc characteristics was obtained. 2.38 ppmw of residual zirconium was calculated based on the reactor mass balance.

Examples Sections IV - Example 10:

Ethylene hexene copolymers were prepared in a 14-inch (35.6 cm) pilot plant scale gas-phase reactor operating at 95 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and with a water-cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 45 lb / hr, hexene was fed to the reactor at a rate of about 0.6 lb / hr (about 0.3 kg / hr), and hydrogen was fed to the reactor at a rate of 6 mPPH. Nitrogen was supplied as a constituent gas to the reactor at about 5 to 8 PPH. The production rate was about 25 PPH. The reactor had a plenum with a recycle airflow of about 1,600 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection nozzle having a tapered diameter of 0.055 inch (1.4 cm) was placed in the plenum air stream. A solution of 1.5 wt% catalyst A in toluene and cocatalyst (MMAO-3A, 1.8 wt% aluminum in 25% heptane / 75% hexane) were mixed in-line and then transferred to the fluidized bed through the injection opening. The MMAO and catalyst were adjusted so that the Al: Zr molar ratio was 350: 1. Nitrogen and isopentane were also fed to the injection nozzle as necessary to maintain a stable average particle size. Nominal 0.4 dg / min (I ₂₁₎ and to give a polymer having a yunimo month 0.934 g / cc properties. 2.27 ppmw of residual zirconium was calculated based on the reactor mass balance.

Examples Sector IV The data of Examples 1 to 10 are summarized in the following Table II.

Examples Section IV - Example 11:

300 pounds (138 kg) of polyethylene (referred to as polymer A) prepared according to Example 4 above was melt-kneaded at a melt temperature of 200 DEG C on a Warner-Plyer ZSK-30 biaxial compressor at 1000 ppm 1068 < / RTI > 1500 ppm) and formed into pellets. The pellets were cast on a Gloucester blown film extrusion line at a rate of 188 lb / hr (85 kg / hr), a melt temperature of 390 ° F (199 ° C), a frost line height of 24 inches (61 cm) And blown into a 1.0 mil (25 mu m) membrane at 60 mil (1524 mu m) in space. Escolen (R) HD 7755.10 (a conventional reactor product series from Exxon Chemical Company, Mount Bellevue, TX) was run under the same conditions for comparison. All membranes were allowed to stand at 23 < 0 > C, 50% humidity for 40 hours. Data are reported in Tables III and IV below.

na is not available for purchase.

Embodiments of Example V of the following Examples utilize a solution feed of a mixed catalyst system comprising a Group 15-containing metal catalyst and a bulky ligand metallocene catalyst.

Example section V.

Solution supply of a mixed catalyst system comprising a Group 15-containing metal catalyst and a bulky ligand metallocene catalyst

Catalyst 1

For the purposes of example section V, Catalyst 1 is indenyl zirconium trispivalate, a bulky ligand metallocene-type compound prepared as described in Example 1.

Preparation of Catalyst 1 - 1 wt%

All procedures were carried out in a glove box.

2. One liter of purified hexane was transferred to a 1 L Erlenmeyer flask equipped with a Teflon coated stir bar.

5. 6.67 g of dry powder of indenyl zirconium trispivalate was added.

6. The solution was placed on a magnetic stirrer and stirred for 15 minutes. All solids were dissolved in the solution.

The solution was poured into a clean, purged 1-L Phytate sample syringe, labeled, removed from the glove box, and placed on the holding site for work.

Catalyst 2

(2, 4, 6-Me ₃ C ₆ H ₂ ) NHCH ₂ CH ₂ ] ₂ NH ligand (ligand 1) and {[(2,4,6-Me ₃ C ₆ H ₂ ) NCH ₂ CH ₂ ] ₂ NH} Zr (CH ₂ Ph) ₂ (Compound I) was prepared as described in Example I part.

Preparation of Catalyst 2 - 1.5% by weight in toluene solution < RTI ID = 0.0 >

Note: All the following procedures were performed in the glove box.

8. In a 1 L Erlenmeyer flask equipped with a Teflon coated stir bar, weigh 100 g of purified toluene.

9. Add 7.28 g of tetrabenzylzirconium.

10. The solution was placed on a stirrer and stirred for 5 minutes. All solids dissolved in the solution.

11. Add 5.42 g of ligand I.

12. Add 551 g of additional purified toluene and stir the mixture for 15 minutes. No solids remained in the solution.

13. The catalyst solution was poured into clean, purged 1-L Phytate sample syringes, labeled, removed from the glove box, and placed in the holding area for operation.

Examples Section V - Example 1:

An ethylene hexene copolymer was prepared in a 14-inch pilot plant scale gas-phase reactor operating at 85 < 0 > C and 350 psig (2.4 MPa) total reactor pressure and equipped with a water-cooled heat exchanger. The reactor had a plenum with a recycle airflow of about 1,600 PPH (plenum is a device used to form a particle lean zone in a fluidized bed gas phase reactor, see U.S. Patent No. 5,693,727). A catalyst injection nozzle having a tapered diameter of 0.055 inch (1.4 cm) was placed in the plenum air stream. Before starting the catalyst supply, the ethylene pressure was about 220 psig (1.5 MPa), the 1-hexene concentration was about 0.3 mol%, and the hydrogen concentration was about 0.12 mol%.

Catalyst 2 was dissolved in a 0.5 wt% solution in toluene and fed to the reactor at 12 cc / hr. Cocatalyst (MMAO-3A, 1 wt% aluminum) was mixed with Catalyst 2 in a feed line and then added to the reactor so that the Al: Zr molar ratio was 400: 1. The production rate was about 24 lb / hr (10.9 kg / hr). In addition, nitrogen was fed at an injection injection rate of 5.0 lb / hr (2.3 kg / hr), 1-hexene 0.1 lb / hr (0.05 kg / hr) and isopentane 0.2 lb / hr (0.09 kg / hr). The flow index of the polymer was 0.31 and the density was 0.935 g / cc. After establishing this, the catalyst feed rate was reduced to 6 cc / hr of catalyst 2 and 0.125 wt% of catalyst 1 during the hexane solution feed was added to the feed line at 13 cc / hr. The entire addition sequence was to add hexane and MMAO mixed with catalyst 1, catalyst 2 solution, followed by adding isopentane and nitrogen. The Al: Zr for the entire system was about 500. Within 6 hours of the addition of catalyst 1, the dual form of the polymer had a nominal 12.9 dg / min (I ₂₁ ), 130 MFR (melt flow rate I ₂₁ / I ₂ ) and a density of 0.953 g / cc. The average particle diameter of the resin was 0.0479 inches (0.12 cm). 0.7 ppmw of residual zirconium was measured by X-ray fluorescence.

All publications mentioned herein are incorporated herein by reference and include any prior art and / or test procedures. While the forms of the invention have been illustrated and described, as apparent from the foregoing general description and specific embodiments, various modifications may be made without departing from the spirit and scope of the invention. It is within the scope of the invention to use two or more Group 15-containing metal compounds with one or more bulky ligand metallocene catalyst systems and / or one or more conventional types of catalyst systems. The present invention is not intended to be limited thereto.

Claims (43)

A process for polymerizing olefin (s) in the presence of a catalyst system comprising a Group 15-containing metal catalyst compound. The method of claim 1, wherein the catalyst system further comprises a bulky ligand metallocene catalyst compound, a conventional transition metal catalyst compound, or a combination thereof. The process of any one of claims 1 to 3, wherein the Group 15-containing metal catalyst compound is a 2 or 3-linked 3 to 14 group catalytic compound. The process of any one of claims 1 to 3, wherein the Group 15-containing hafnium catalyst compound is a Group 3 to Group 14 metal atom bonded to at least one leaving group and to at least two Group 15 atoms, wherein at least two At least one of the Group 15 atoms is bonded to a Group 15 or Group 16 atom through a bridging group and preferably the bridging group is selected from the group consisting of a C ₁ to C ₂₀ hydrocarbon group, a heteroatom-containing group, silicon, germanium, tin, ≪ / RTI > 5. The compound of claim 4, wherein the Group 15 or Group 16 atoms also do not bind to anything or be bonded to a hydrogen, Group 14 atom-containing group, halogen or heteroatom-containing group, And optionally bonded to a hydrogen, halogen, heteroatom or hydrocarbyl group or a heteroatom-containing group. 6. A process according to any one of claims 1 to 5, wherein the Group 15-containing compound is represented by the formula (I) or (II). (I) ≪ RTI ID = 0.0 & In this formula, M is a Group 3 to Group 14 metal, preferably a Group 3 to Group 7 metal, more preferably a Group 4 to 6 metal; Each X is independently a leaving group; y is 0 or 1; n is the oxidation state of M; m is the type charge of the YZL or YZL 'ligand; L is an element of Group 15 or Group 16; L 'is a Group 15 or Group 16 element or Group 14-containing group; Y is a Group 15 element; Z is a Group 15 element; R ¹ and R ² are independently a C ₁ to C ₂₀ hydrocarbon group, a heteroatom-containing group having up to 20 carbon atoms, silicon, germanium, tin, lead or phosphorus; R ³ is absent or is a hydrocarbon group, a hydrogen, a halogen, a heteroatom-containing group; R ⁴ and R ⁵ are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group, or a multiple ring system; R < ¹ > and R < ² > may be interconnected (to each other) with respect to each other, and R < ⁴ > and R < ⁵ > R ⁶ and R ⁷ are not independently present or are hydrogen, an alkyl group, a halogen, a heteroatom or a hydrocarbyl group; R ^* is absent or is hydrogen, a Group 14 atom-containing group, a halogen, a heteroatom-containing group. The method according to claim 6, wherein R ⁴ and R ⁵ are represented by the following formula (1). [Chemical Formula 1] In this formula, R ⁸ to R ¹² each independently represent a hydrogen atom, a C ₁ to C ₄₀ alkyl group, a halide, a hetero atom, a heteroatom-containing group containing not more than 40 carbon atoms, preferably a C ₁ to C ₂₀ linear or branched alkyl group , Preferably a methyl, ethyl, propyl or butyl group, and any two R groups may form a cyclic group and / or a heterocyclic group, and the cyclic group may be aromatic. The method of claim 7, R ^9, R ¹⁰ and R ¹² are independently methyl, ethyl, propyl or butyl group, or, R ^9, R ¹⁰ and R ¹² is a methyl group, R ⁸ and R ¹¹ is a hydrogen method. A compound according to any one of claims 6 to 8, wherein L, Y and Z are independently nitrogen, R ¹ and R ² are hydrocarbon radicals, R ³ is hydrogen, R ⁶ and R ⁷ are absent, L and Z are independently nitrogen, L 'is a hydrocarbyl radical, R ⁶ and R ⁷ is a method that does not exist. The process of any one of claims 1 to 9 wherein the Group 15-containing metal catalyst compound contains at least one substituted hydrocarbon leaving group having at least 6 carbon atoms, preferably wherein at least one substituted hydrocarbon leaving group Lt; / RTI > is an aryl substituted alkyl group, most preferably the aryl substituted alkyl group is benzyl. A process according to any one of claims 1 to 10, wherein the catalyst system further comprises an activator (s). The process according to any one of claims 1 to 11, wherein the catalyst compound (s) and / or activator compound (s) are introduced into the gas phase or slurry phase reactor of the liquid carrier. 13. The process of claim 12, wherein at least two catalysts and at least one activator are introduced into the reactor in the liquid carrier, each catalyst is independently activated and the catalyst and activator (s) are combined in the liquid carrier and introduced into the reactor Way. 14. The method of claim 13, wherein the catalyst is sequentially activated. 14. The method of claim 13, i) the catalyst is compounded in a liquid carrier and then the activator (s) is introduced into the liquid carrier; ii) the catalyst is introduced into the linking means which is combined in the liquid carrier and connected to the reactor, and then the activator (s) is introduced into the linking means at the same or different location as the catalyst. A process according to any one of claims 12 to 15, wherein the liquid carrier containing catalyst (s) and activator (s) is disposed in a device for introducing the liquid carrier into the reactor. 17. The process according to claim 16, wherein the catalyst and the liquid carrier are introduced into the apparatus before the activator is introduced into the apparatus. 13. A process according to claim 12 or claim 17 wherein the liquid carrier comprises a liquid stream flowing or being sprayed into the reactor. A process as claimed in any one of claims 12 to 18, wherein at least one catalyst, at least one activator and a liquid carrier are arranged in the apparatus for introduction into the reactor, the first catalyst and activator being introduced into the apparatus, Wherein the catalyst (s) are introduced into the apparatus. 13. The method of claim 12, i) a first formulation comprising at least one catalyst in a liquid carrier is introduced into an apparatus connected to the reactor and a second composition comprising at least one activator in the liquid carrier is introduced into the apparatus connected to the reactor, Afterwards, a different catalyst in the liquid carrier is introduced into the apparatus connected to the reactor, and then the catalyst-activator combination is introduced into the reactor; ii) at least one catalyst (a) and at least one activator (a) are combined in a liquid carrier, at least one catalyst (b) and at least one activator (b) are combined in a liquid carrier, b) is different from (a) catalyst (a) or (b) activator (b) is different from activator (a) and then the two compounds are introduced into an apparatus connected to the reactor and then the compounds are introduced into the reactor; iii) introducing the liquid carrier containing the catalyst (a) and the catalyst (b) into an apparatus connected to the reactor, and then introducing the liquid carrier containing the catalyst (b) and the activator (b) into the apparatus connected to the reactor; iv) placing a first composition comprising at least one catalyst (a), at least one activator (a) and a liquid carrier in an apparatus connected to the reactor, and then at least one catalyst (b), at least one activator (b) and the liquid carrier (catalyst (b) and / or activator (b) are different from catalyst (a) and / or activator (a) And then introducing the compounded composition into the reactor; v) placing at least one catalyst and a liquid carrier in the apparatus for introducing the catalyst into the reactor, introducing additional catalyst (s) and activator (s) into the apparatus after the first catalyst has been introduced into the apparatus, vi) introducing a first composition comprising at least one catalyst (a), at least one activator (a) and a liquid carrier into the feeder to the reactor, and then feeding the second catalyst in the liquid carrier to the reactor And then adding a second activator in the liquid carrier to the feeder to the reactor, and then introducing the entire formulation into the reactor. The process according to claim 12, wherein the catalyst compound (s) and / or activator (s) are combined prior to being disposed in the liquid carrier and / or the carrier is an alkane, preferably pentane, hexane and / Way. The method of any one of claims 1-11, wherein the catalyst compound (s) and / or activator compound (s) are supported on the carrier (s). 23. The process of claim 22, wherein the activator is an alkyl aluminum compound, an alumoxane, a modified alumoxane, a non-coordinating anion, a borane, a borate ionizing compound and / or a Lewis acid aluminum containing activator represented by formula VII: (VII) R _{n is} Al (ArHal) _3-n In this formula, R is a monoanionic ligand; ArHal is a halogenated C ₆ aromatic or higher carbon number polycyclic aromatic hydrocarbon or aromatic ring assembly wherein two or more rings (or fused ring systems) are bonded to each other directly or together; n is 1 to 2, preferably n is 1. The method of any one of claims 1 to 23, wherein the continuous gas phase process and the continuous slurry phase process are selected from the group consisting of the continuous gas phase process and the continuous slurry phase process. The process according to any one of claims 1 to 24, wherein the olefin (s) is ethylene or propylene, or ethylene and at least one other monomer having from 3 to 20 carbon atoms. 15. A catalyst system comprising a Group 15-containing metal catalyst compound, an activator, and optionally a carrier. 27. The catalyst system of claim 26, further comprising a bulky ligand metallocene catalyst compound, a conventional transition metal catalyst compound, or combinations thereof. 26. The catalyst system according to claim 26 or 27, wherein the Group 15-containing metal catalyst compound is a Group 15-containing 2-or 3-membered Group 3 to Group 14 metal catalyst compound. The process of any one of claims 26 to 28, wherein the 15-group containing hafnium catalyst compound and, when present, the bulky ligand metallocene catalyst compound are contacted with an activator to form a reaction product, Catalyst system. 29. A process according to any one of claims 26 to 29, wherein the system is supported on a carrier and the activator is a Lewis acid aluminum containing activator represented by formula VII. (VII) R _{n is} Al (ArHal) _3-n In this formula, R is a monoanionic ligand; ArHal is a halogenated C ₆ aromatic or higher carbon number polycyclic aromatic hydrocarbon or aromatic ring assembly wherein two or more rings (or fused ring systems) are bonded to each other directly or together; n is 1 to 2, preferably n is 1. Use of Group 15-containing Group 3 to Group 14 metal catalyst compounds to produce high molecular weight components in multimodal polymer compositions. Use of a bulky ligand metallocene catalyst compound to produce a low molecular weight component in a multimodal polymer composition. 3. The method of claim 2, wherein the bulky ligand metallocene compound is represented by the formula (VI). (VI) L ^D MQ ₂ (YZ) X _n Wherein M is a Group 3 to Group 16 metal, preferably a Group 4 to 6 metal; L ^D is a bulky ligand bonded to M, preferably an indenyl or fluorenyl group; Each Q is a monovalent anionic ligand bound to M; Q ₂ (YZ) forms a single charged multidentate ligand; when n is 2, X is a monovalent anionic group, or when n is 1, X is a divalent anionic group; n is 1 or 2; 34. The method of claim 33, wherein X is a carbamoyl, carboxylate or other heteroallyl moiety represented by a combination of QYZ. The process of claims 2 or 33, wherein the molar ratio of the Group 15-containing metal compound to the bulky ligand metallocene compound is from 1:99 to 99: 1, preferably from 20:80 to 80:20. (Having) a density of about 0.89 to 0.97 g / cm < ³ > and having an I ₂₁ of about 1 to 10 dg / min or less and having I ₂ of about 0.01 to 1000 dg / Containing ligand that is capable of being detected with a high-resolution mass spectrometer having an I ₂₁ / I ₂ of greater than or equal to 180,000 M _w and having (or have) a ash content of less than 100 ppm , ≪ / RTI > 2, and 33 to < RTI ID = 0.0 > 35. ≪ / RTI > At least two ash content of less than I ₂₁ / I _2, 100 ppm of greater than 80, is prepared in a single reactor with a catalyst, and (or) an ethylene polymer composition of the base material having a 0.945 g / cm ³ or more density polyethylene. 38. The composition of claim 37, wherein the polymer has an extrusion rate of greater than about 17 lb / hr / inch (mold circumference) (2.8 Kg / hr / cm (mold circumference)). The method of claim 37, wherein the film has a turbidity of 60% or less or a 45 占 gloss of 13 or more when formed of a film having a thickness of 0.5 mil (13 占 퐉), and the film is a blowing film or a cast film, The membrane preferably has a MD Tear of about 5 g / mil (0.20 g / m) to 25 g / mil (1.0 g / m). An ethylene polymer or copolymer having a zirconium residual metal content of less than 2.0 ppm, an I ₂₁ of 12 or less, a residual nitrogen content of I ₂₁ / I _{2 of} 80 or greater and / or a residual nitrogen content of less than or equal to 2.0 ppm, and / . A membrane produced by extruding, blowing or casting a membrane from a polymer produced by the method of claim 12. A composition comprising polyethylene produced by the process of claim 12 having a density of 0.910 to 0.935 g / cc, a melt index of 10 dg / min or less, a haze of 10% or less and a 45 degree gloss of 60 units or more. 43. The method of claim 42, wherein the polyethylene has a density of 0.915 to 0.930 g / cc and / or has a melt index of 5 dg / min or less and / or has a turbidity of 7% (Or have) an Elmendorf tear of greater than or equal to 100 grams (having an Elmendorf tear of 100 g or more) having a dart impact strength of at least 150 g (measured according to ASTM D 1709 Method A) Or having a transverse Elmendorf tear strength of at least 500 grams.