Catalyst composition, method of polymerization, and polymer therefrom

Abstract

catalyst compositions and methods, useful in polymerization processes, utilizing at least two metal compounds are disclosed. At least one of the metal compounds is a group 15 containing metal compound and the other metal compound is preferably a bulky ligand metallocene-type catalyst. The invention also discloses a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.

Description

FIELD OF THE INVENTION

The present invention relates to a catalyst composition comprising at least two metal compounds useful in olefin polymerization processes to produce polyolefins. Preferably, at least one of the metal compounds is a Group 15 containing metal compound. More preferably, the other metal compound is a bulky ligand metallocene-type catalyst. The present invention also relates to a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.

BACKGROUND OF THE INVENTION

Polyethylenes with a higher density and higher molecular weight are valued in film applications requiring high stiffness, good toughness and high throughput. Such resins are also valued in pipe applications requiring stiffness, toughness and long-term durability, and particularly resistance to environmental stress cracking.

Typical metallocene polymerization catalysts (i.e. those containing a transition metal bound, for example, to at least one cyclopentadienyl, indenyl or fluorenyl group) have recently been used to produce resins having desirable product properties. While these resins have excellent toughness properties, particularly dart impact properties, they, like other metallocene catalyzed polyethylenes, can be difficult to process, for example, on older extrusion equipment. One of the means used to improve the processing of such metallocene catalyzed polyethylenes is to blend them with another polyethylene. While the two polymer blend tends to be more processable, it is expensive and adds a cumbersome blending step to the manufacturing/fabrication process.

Higher molecular weight confers desirable mechanical properties and stable bubble formation onto polyethylene polymers. However, it also inhibits extrusion processing by increasing backpressure in extruders, promotes melt fracture defects in the inflating bubble and potentially, promotes too high a degree of orientation in the finished film. To remedy this, one may form a secondary, minor component of lower molecular weight polymer to reduce extruder backpressure and inhibit melt fracture. Several industrial processes operate on this principle using multiple reactor technology to produce a processable bimodal molecular weight distribution (MWD) high density polyethylene (HDPE) product HIZEX™, a Mitsui Chemicals HDPE product, is considered the worldwide standard. HIZEX™ is produced in two or more reactors and is costly to produce. In a multiple reactor process, each reactor produces a single component of the final product.

Others in the art have tried to produce two polymers together at the same time in the same reactor using two different catalysts. PCT patent application WO 99/03899 discloses using a typical metallocene catalyst and a conventional Ziegler-Natta catalyst in the same reactor to produce a bimodal MWD HDPE. Using two different types of catalysts, however, result in a polymer whose characteristics cannot be predicted from those of the polymers that each catalyst would produce if utilized separately. This unpredictability occurs, for example, from competition or other influence between the catalyst or catalyst systems used. These polymers however still do not have a preferred balance of processability and strength properties. Thus, there is a desire for a combination of catalysts capable of producing processable polyethylene polymers in preferably a single reactor having desirable combinations of processing, mechanical and optical properties.

SUMMARY OF THE INVENTION

The present invention provides a catalyst composition, a polymerization process using the catalyst composition, polymer produced therefrom and products made from the polymer.

In one embodiment, the invention is directed to a catalyst composition including at least two metal compounds, where at least one metal compound is a Group 15 containing metal compound, and where the other metal compound is a bulky ligand metallocene-type compound, a conventional transition metal catalyst, or combinations thereof.

In one embodiment, the invention is directed to a catalyst composition including at least two metal compounds, where at least one metal compound is a Group 15 containing bidentate or tridentate ligated Group 3 to 14 metal compound, preferably a Group 3 to 7, more preferably a Group 4 to 6, and even more preferably a Group 4 metal compound, and where the other metal compound is a bulky ligand metallocene-type compound, a conventional transition metal catalyst, or combinations thereof In this embodiment it is preferred that the other metal compound is a bulky ligand metallocene-type compound.

In another embodiment, the invention is directed to a catalyst composition including at least two metal compounds, where one metal compound is a Group 3 to 14 metal atom bound to at least one leaving group and also bound to at least two Group 15 atoms, at least one of which is also bound to a Group 15 or 16 atom through another group, and where the second metal compound, is different from the first metal compound, and is a bulky ligand metallocene-type catalyst, a conventional-type transition metal catalyst, or combinations thereof.

In an embodiment, the invention is directed to processes for polymerizing olefin(s) utilizing the above catalyst compositions, especially in a single polymerization reactor.

In yet another embodiment, the invention is directed to the polymers prepared utilizing the above catalyst composition, preferably to a new bimodal MWD HDPE.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The present invention relates to the use of a mixed catalyst composition where one of the catalysts is a Group 15 containing metal compound. Applicants have discovered that using these compounds in combination with another catalyst, preferably a bulky ligand metallocene type compound, produces a new bimodal MWD HDPE product. Surprisingly, the mixed catalyst composition of the present invention may be utilized in a single reactor system.

Group 15 Containing Metal Compound

The mixed catalyst composition of the present invention includes a Group 15 containing metal compound. The Group 15 containing compound generally includes a Group 3 to 14 metal atom, preferably a Group 3 to 7, more preferably a Group 4 to 6, and even more preferably a Group 4 metal atom, bound to at least one leaving group and also bound to at least two Group 15 atoms, at least one of which is also bound to a Group 15 or 16 atom through another group. In one preferred embodiment, at least one of the Group 15 atoms is also bound to a Group 15 or 16 atom through another group which may be a C₁ to C₂₀ hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, or phosphorus, wherein the Group 15 or 16 atom may also be bound to nothing or a hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group, and wherein each of the two Group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.

In a preferred embodiment, the Group 15 containing metal compound of the present invention may be represented by the formulae: ##STR00001##
wherein

• • M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, preferably a Group 4, 5, or 6 metal, and more preferably a Group 4 metal, and most preferably zirconium, titanium or hafnium,
  • each X is independently a leaving group, preferably, an anionic leaving group, and more preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and most preferably an alkyl.
  • y is 0 or 1 (when y is 0 group L′ is absent),
  • n is the oxidation state of M, preferably +3, +4, or +5, and m or e preferably +4,
  • m is the formal charge of the YZL or the YZL′ ligand, preferably 0, −1, −2 or −3, and more preferably −2,
  • L is a Group 15 or 16 element, preferably nitrogen,
  • L′ is a Group 15 or 16 element or Group 14 containing group, preferably carbon, silicon or germanium,
  • Y is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen,
  • Z is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen,
  • R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus, preferably a C₂ to C₂₀ alkyl, aryl or
    where

    These bridged compounds represented by formula (IV) are known as bridged, bulky ligand metallocene-type catalyst compounds. L^A, L^B,
    where
    where,

  • Density was measured according to ASTM D 1505.
  • Melt Index (MI) I₂ was measured according to ASTM D-1238, Condition E, at 190° C.
  • I₂₁ was measured according to ASTM D-1238, Condition F, at 190° C.
  • Melt Index Ratio (MIR) is the ratio of I₂₁, over I₂.
  • Weight % comonomer was measured by proton NMR.
  • Dart Impact was measured according to ASTM D 1709.
  • MD and TD Elmendorf Tear were measured according to ASTM D 1922.
  • MD and TD 1% Secant modulus were measured according to ASTM D 882.
  • MD and TD tensile strength and ultimate tensile strength were measured according to ASTM D882.
  • MD and TD elongation and ultimate elongation were measured according to ASTM D 412.
  • MD and TD Modulus were measured according to ASTM 882-91.
  • Haze was measured according to ASTM 1003-95, Condition A.
  • 45° gloss was measured according to ASTM D 2457.
  • BUR is blow up ratio.
  • “PPH” is pounds per hour. “mPPH” is millipounds per hour. “ppmw” is parts per million by weight.
  • Indenyl zirconium tris pivalate, a bulky ligand metallocene-type compound, also represented by formula VI, can be prepared by performing the following general reactions:
    Zr(NEt₂)₄+IndH→IndZr(NEt₂)₃+Et₂NH   (1)
    IndZr(NEt₂)₃+3(CH₃)₃COO₂H→IndZr[O₂OC(CH₃)]₃+Et₂NH   (2)

  Where Ind=indenyl and Et is ethyl.

  Preparation of [(2,4,6-Me₃C₆H₂)NHCH₂CH₂]₂NH Ligand (Ligand I)

  A 2 L one-armed Schlenk flask was charged with a magnetic stir bar, diethylenetriamine (23.450 g, 0.227 mol), 2-bromomesitylene (90.51 g, 0.455 mol), tris (dibenzylideneacetone)dipalladium (1.041 g, 1.14 mmol), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemic BINAP) (2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol), and toluene (800 mL) under dry, oxygen-free nitrogen. The reaction mixture was stirred and heated to 100 C. After 18 h the reaction was complete, as judged by proton NMR spectroscopy. All remaining manipulations can be performed in air. All solvent was removed under vacuum and the residues dissolved in diethyl ether (1 L). The ether was washed with water (3×250 mL) followed by saturated aqueous NaCl (180 g in 500 mL) and dried over magnesium sulfate (30 g). Removal of the ether in vacuo yielded a red oil which was dried at 70 C for 12 h under vacuum (yield: 71.10 g, 92%). ¹H NMR (C₆D₆) δ 6.83 (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

  Preparation of 1.5 wt % Catalyst A in Toluene Solution

  Note: All procedures below were performed in a glove box.

  • 1. Weighed out 100 grams of purified toluene into a 1 L Erlenmeyer flask equipped with a Teflon coated stir bar.
  • 2. Added 7.28 grams of Tetrabenzyl Zirconium.
  • 3. Placed solution on agitator and stirred for 5 minutes. All of the solids went into solution.
  • 4. Added 5.42 grams of Ligand I.
  • 5. Added an additional 551 grains of purified toluene and allowed mixture to stir for 15 minutes. No solids remained in the solution.
  • 6. Poured catalyst solution into a clean, purged 1-L Whitey sample cylinder, labeled, removed from glovebox and placed in holding area for operations.
    Alternate Preparation of Compound I {[(2,4,6-Me₃C₆H₂) NCH₂CH₂]₂NH}Zr(CH₂Ph)₂

  A 500 mL round bottom flask was charged with a magnetic stir bar, tetrabenzyl zirconium (Boulder Scientific) (41.729 g, 91.56 mmol), and 300 mL of toluene under dry, oxygen-free nitrogen. Solid ligand I above (32.773 g, 96.52 mmol) was added with stirring over 1 minute (the desired compound precipitates). The volume of the slurry was reduced to 100 mL and 300 mL of pentane added with stirring. The solid yellow-orange product was collected by filtration and dried under vacuum (44.811 g, 80% yield). ¹H NMR (C₆D₆) δ 7.22-6.81 (m, 12), 5.90 (d, 2), 3.38 (m, 2), 3.11 (m, 2), 3.01 (m, 1), 2.49 (m, 4), 2.43 (s, 6), 2.41 (s, 6), 2.18 (s, 6), 1.89 (s, 2), 0.96 (s, 2).

  Preparation of Catalyst B

  Preparation 1 wt % Catalyst B in Hexane Solution

  All procedures were performed in a glove box.

  • 1. Transfer 1 liter of purified hexane into a 1 L Erlenmeyer flask equipped with a Teflon coated stir bar.
  • 2. Add 6.67 grams of indenyl zirconium tris pivalate dried powder.
  • 3. Place solution on magnetic agitator and stir for 15 minutes. All of the solids go into solution.
  • 4. Pour solution into a clean, purged 1-L Whitey sample cylinder, labeled, and removed from glovebox and place in holding area until use in operation.

  Comparative Example 1

  An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C. and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 40 pounds per hour (18.1 kg/hr), hexene was fed to the reactor at a rate of about 0.6 pounds per hour (0.27 kg/hr) and hydrogen was fed to the reactor at a rate of 5 mPPII. Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. The production rate was about 27 PPH. The reactor was equipped with a plenum having about 1,900 PPH of recycle gas flow. (The plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor, as described in detail in U.S. Pat. No. 5,693,727 which is incorporated herein by reference.) A tapered catalyst injection nozzle having a 0.041 inch (0.10 cm) hole size was positioned in the plenum gas flow. A solution of 1 wt % of Catalyst A in toluene and cocatalyst (MMAO-3A, 1 wt % Aluminum) were mixed in line prior to passing through the injection nozzle into the fluidized bed. (MMAO-3A is modified methyl alumoxane in heptane, commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A .) MMAO to catalyst was controlled 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 (I₂₁) and 0.935 g/cc (density) properties was obtained. A residual zirconium of 1.63 ppmw was calculated based on a reactor mass balance.

  Comparative Example 2

  An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 80° C. and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 37 pounds per hour (19.8 kg/hr), hexene was fed to the reactor at a rate of about 0.4 pounds per hour (0.18 kg/hr) and hydrogen was fed to the reactor at a rate of 12 mPPH. Ethylene was fed to maintain 180 psi (1.2 MPa) ethylene partial pressure in the reactor. The production rate was about 25 PPH. The reactor was equipped with a plenum having about 1,030 PPH of recycle gas flow. (The plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor.) A tapered catalyst injection nozzle having a 0.055 inch (0.14 cm) hole size was positioned in the plenum gas flow. 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. The Catalyst B and hexene mixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a line for about 40 minutes. In addition to the solution, isopentane and nitrogen were added to control particle size. The total system was passed through the injection nozzle into the fluidized bed. MMAO to catalyst ratio was controlled so that the Al:Zr molar ratio was 300:1. A bimodal polymer was produced which was 797 g/10 min melt index. The density was 0.9678 g/cc. A residual zirconium of 0.7 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 4 floury distributions was completed and the results are shown in Table I.

  Example 3

  An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 80° C. and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 53 pounds per hour (24 kg/hr), hexene was fed to the reactor at a rate of about 0.5 pounds per hour (0.22 kg/hr) and hydrogen was fed to the reactor at a rate of 9 mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor. The production rate was about 25 PPH. The reactor was equipped with a plenum having about 990 PPH of recycle gas flow. (The plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor.) A tapered catalyst injection nozzle having a 0.055 inch (0.12) hole size was positioned in the plenum gas flow. 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. The Catalyst B and hexene mixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a line for about 20-25 minutes. In a separate activating stainless steel tube, a 1 wt % Catalyst A in toluene solution was activated with cocatalyst (MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes. The two independently activated solutions were combined into a single process line for about 4 minutes. The quantity of Catalyst A catalyst was about 40-45 mol % of the total solution fed. In addition to the solution, isopentane and nitrogen were added to control particle size. The total system was passed through the injection nozzle into the fluidized bed. MMAO to catalyst ratio was controlled so that the Al:Zr molar ratio was 300:1. A bimodal polymer was produced which was 0.045 g/10 min melt index and 7.48 g/10 min flow index. The density was 0.9496 g/cc. A residual zirconium of 1.7 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.

  Example 4

  An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C. and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 50 pounds per hour (22.7 kg/hr), some of the hexene was fed to the reactor at a rate of about 0.7 pounds per hour (0.32 kg/hr) and hydrogen was fed to the reactor at a rate of 11 mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor. The production rate was about 29 PPH. The reactor was equipped with a plenum having about 970 PPH of recycle gas flow. (The plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor.) A tapered catalyst injection nozzle having a 0.055 inch (0.14 cm) hole size was positioned in the plenum gas flow. 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. The Catalyst B and hexene mixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a line for about 20-25 minutes. In a separate activating stainless steel tube, a 1 wt % Catalyst A in toluene solution was activated with cocatalyst (MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes. The two independently activated solutions were combined into a single process line for about 4 minutes. The quantity of Catalyst A catalyst was about 40-45 mol % of the total solution fed. In addition to the solution, isopentane and nitrogen were added to control particle size. The total system was passed through the injection nozzle into the fluidized bed. MMAO to catalyst was controlled so that the Al:Zr molar ratio was 300:1. A bimodal polymer was produced which was 0.054 g/10 min melt index and 7.94 g/10 min flow index. The density was 0.948 g/cc. A residual zirconium of 1.1 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.

  Example 5

  An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C. and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 60 pounds per hour (27.2 kg/hr), hexene was fed to the reactor at a rate of about 0.8 pounds per hour (0.36 kg/hr) and hydrogen was fed to the reactor at a rate of 13 mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor. The production rate was about 34 PPH. The reactor was equipped with a plenum having about 960 PPH of recycle gas flow, (The plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor.) A tapered catalyst injection nozzle having a 0.055 inch (0.14 cm) was positioned in the plenum gas flow. 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. The Catalyst B and hexene mixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a line for about 20-25 minutes. In a separate activating stainless steel tube, a 1 wt % Catalyst A in toluene solution was activated with cocatalyst (MMAO-3A, 1 wt % Aluminum) for about 50-55 minutes. The two independently activated solutions were combined into a single process line for about 4 minutes. The quantity of Catalyst A catalyst was about 40-45 mol % of the total solution fed. In addition to the solution, isopentane and nitrogen were added to control particle size. The total system was passed through the injection nozzle into the fluidized bed. MMAO to catalyst ratio was controlled so that the Al:Zr molar ratio was 300:1. A bimodal polymer was produced which was 0.077 g/10 min melt index and 12.7 g/10 min flow index. The density was 0.9487 g/cc. A residual zirconium of 0.9 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.

  Example 6

  An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm) pilot plant scale gas phase reactor operating at 85° C. and 320 psig (2.2 MPa) total reactor pressure having a water cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 60 pounds per hour (27.2 kg/hr), hexene was fed to the reactor at a rate of about 0.8 pounds per hour (0.36 kg/hr) and hydrogen was fed to the reactor at a rate of 13 mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor. The production rate was about 34 PPH. The reactor was equipped with a plenum having about 1,100 PPH of recycle gas flow. (The plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor.) A tapered catalyst injection nozzle having a 0.055 inch (0.14 cm) was positioned in the plenum gas flow. 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. The Catalyst B and hexene mixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a line 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 being sprayed into the reactor. The quantity of Catalyst A catalyst was about 40-45 mol % of the total solution fed. In addition to the solution, isopentane and nitrogen were added to control particle size. The total system was passed through the injection nozzle into the fluidized bed. MMAO to catalyst ratio was controlled so that the final Al:Zr molar ratio was 300:1. A bimodal polymer was produced which was 0.136 g/10 min melt index and 38.1 g/10 min flow index. The density was 0.9488 g/cc. A residual zirconium of 0.5 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.

  Example 7

  An ethylene-hexene copolymer was produced in a 14-inch (35.6 cm)pilot plant scale gas phase reactor operating at 85° C. and 350 psig (2.4 MPa) total reactor pressure having a water cooled heat exchanger. Ethylene was fed to the reactor at a rate of about 42 pounds per hour (19.1 kg/hr), hexene was fed to the reactor at a rate of about 0.8 pounds per hour (0.36 kg/hr) and hydrogen was fed to the reactor at a rate of 13 mPPH. Ethylene was fed to maintain 220 psi (1.52 MPa) ethylene partial pressure in the reactor. The production rate was about 32 PPH. The reactor was equipped with a plenum having about 2010 PPH of recycle gas flow. (The plenum is a device used to create a particle lean zone in a fluidized bed gas-phase reactor.) A tapered catalyst injection nozzle having a 0.055 inch (0.14 cm) was positioned in the plenum gas flow. 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. The Catalyst B and hexene mixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum) in a line for about 15 minutes. 0.5 wt % Catalyst A in toluene solution was added to the activated Catalyst B solution for about 15 minutes before being sprayed into the reactor. The quantity of Catalyst A catalyst was about 65-70 mol % of the total solution fed. In addition to the solution, isopentane and nitrogen were added to control particle size. The total system was passed through the injection nozzle into the fluidized bed. MMAO to catalyst ratio was controlled so that the final Al:Zr molar ratio was 500. A bimodal polymer was produced which was 0.06 g/10 min melt index and 6.26 g/10 min flow index. The density was 0.9501 g/cc. A residual zirconium of 0.65 ppmw was calculated based on a reactor mass balance. SEC analysis and deconvolution using 7-8 floury distributions was completed and the results are shown in Table I.

  TABLE I
  Example	1 (Comp)	2 (Comp)	3	4	5	6	7
  I21 (dg/min)	0.28	n/a	7.5	7.94	12.6	38.1	6.26
  I21/I2	—	—	165.3	147	164.6	280.4	104
  I2 (dg/min)	no flow	797	0.045	0.054	0.077	0.136	0.060
  Experimental SEC Data
  Mn	80,600	2,952	7,908	10,896	10,778	10,282	8,700
  Mw	407,375	13,398	340,011	263,839	259,389	261,138	287,961
  Mw/Mn	5.05	4.54	43	24.2	24.1	25.4	33.10
  Mn (calculated)	—	—	7,645	10,552	10,673	10,105	8,523
  Mw (calculated)	—	—	339,752	258,282	248,215	252,310	284,814
  Mw/Mn (calculated)	—	—	44.44	24.48	23.26	24.97	33.42
  LMW Mn (calculated)	—	2,988	3,741	5,548	5,731	6,382	4,165
  LMW Mw (calc.)	—	13,214	13,259	16,388	25,214	18,333	11,771
  LMW Mw/Mn (calc.)	—	4.42	3.54	2.95	2.65	2.87	2.83
  HMW Mn (calculated)	73,979	—	122,758	111,256	85,461	88,374	115,954
  HMW Mw (calc.)	407,513	—	633,154	501,013	484,657	607,625	526,630
  HMW Mw/Mn (calc.)	5.51	—	5.16	4.50	5.67	6.88	4.54
  SPLIT (HMW/Total)	100.00	0.00	52.67	49.92	49.64	39.70	53.03
  Reactor Conditions
  Reactor Temp (° C.)	85	80	80	85	85	85	85
  C2 psi/Mpa	220/1.52	180/1.24	220/1.52	220/1.52	220/1.52	220/1.52	220/1.52
  H2/C2 mole ratio	0.0016	0.0018	0.0013	0.0014	0.0014	0.0010	0.0019
  C6/C2 mole ratio	0.00488	0.00153	0.0074	0.0073	0.0077	0.0075	0.0050
  Residence time (hr)	3.6	7.5	5.3	4.74	3.87	3.87	3.4
  Molar ratio	—	—	0.71	0.73	0.76	0.76	2.16
  HMW/LMW
  Molar % Catalyst A	100	—	41	42	43	43	68
  Zr ppm, by lab	—	—	1.33	1.61	1.33	0.8	0.97
  Zr ppm, by feed	1.63	—	1.46	1.06	0.9	0.54	0.62
  Average	1.63	—	1.40	1.34	1.12	0.67	0.80
  Al/Zr mole ratio	400	—	330	380	320	307	500
  Catalyst B activity g	—	—
  PE/mmol cat-hr			9,965	12,515	18,754	37,288	50,142
  Catalyst A activity g	—	—
  PE/mmol cat-hr	15,559	—	15,730	17,042	24,323	32,465	26,203

  Comparative Examples 1 and 2 give experimental data on how the single component catalyst system behave. Examples 3 and 4 demonstrate the effect of temperature on essentially the same reactor conditions and catalyst feed system. Note that at higher temperature, the M_w/M_n is lower, as is the MFR. Examples 5 and 6 compare the effect of activation scheme for essentially the same reactor conditions and catalyst feed system. Note that in Example 6, the overall activity of the catalyst is better. However, the amount of high molecular weight material produced is lower. Examples 6 and 7 demonstrate the ability to control the amount of high molecular weight material produced at essentially similar reactor conditions. Example 7 fed a higher percentage of Catalyst A feed, hence a higher quantity of higher Mw material was produced.

  Example 8

  350 pounds (159 kg) of polyethylene produced according to example 4 above (referred to as Polymer A) was compounded on a Wemer-Fleiderer ZSK-30 twin screw extruder with 1000 ppm Irganox™ 1076 and 1500 ppm Irgafos™ 1068 at a melt temperature of 220° C. and formed into pellets. Then the pellets were blown into a 0.5 mil (13 μm) film on an Alpine blown film extrusion line. The extrusion condition were: die-160 mm triplex, 1.5 mm die gap, 400° C. die temperature, 48 inches (122 cm) layflat width, target melt temperature—410° F. (210° C.), and extrusion rates—310 lb/hr (144 kg/hr), 420 lb/hr (191 kg/hr) and 460 lb/hr (209 kg/hr). ESCORENE™ HD7755.10 (a conventional series reactor product of Exxon Chemical Company, Houston, Tex.) was run at the same conditions as a comparison. All films were conditioned according to 23° C., 50% humidity for 40 hours. The data are reported in Table A.

  	TABLE A
  	Polymer A	HD7755.10	Polymer A	HD7755.10	Polymer A	HD7755.10
  Rate lb/hr/	317 (144)	317 (144)	421 (191)	421 (191)	460 (209)	460 (209)
  (kg/hr)
  Film Gage	0.524 mil/	0.502 mil/	0.532 mil/	0.519 mil/	0.543 mil/	0.528 mil/
  	13 μm	13 μm	14 μm	13 μm	14 μm	13 μm
  Density g/cc	0.9489	0.949	0.9502	0.949	0.9468	0.9489
  26″ (66 cm)	355 g	308 g	327 g	325 g	nm	nm
  dart @ 1 day
  26″ (66 cm)	351 g	308 g	314 g	344 g	301 g	360 g
  dart @ 7 days
  MD Tear	22 (0.87)	16 (0.63)	25 (0.98)	15 (0.59)	22 (0.87)	15 (0.59)
  g/mil (g/μ)
  TD Tear	97 (3.82)	102 (4.02)	77 (3.03)	84 (3.31)	100 (3.94)	81 (3.19)
  g/mil (g/μ)
  1% Secant	161,000	200,200	159,000	183,800	156,200	178,700
  MD, psi (MPa)	(1110)	(1380)	(1096)	(1267)	(1077)	(1232)
  1% Secant	184,500	212,500	163,500	206,600	161,400	212,500
  TD, psi (MPa)	(1272)	(1465)	(1127)	(1425)	(1113)	(1465)
  MD UT Str.	14445	14347	12574	15110	12934	15609
  psi (MPa)	(100)	(99)	(87)	(104)	(89)	(108)
  TD UT Str.	13369	12124	10785	12278	11727	11482
  psi (MPa)	(92)	(84)	(74)	(85)	(81)	(79)
  U Elong. %	285	293	246	296	253	299
  U Elon. %	317	393	305	377	340	377
  Haze %	59.6	64.0	57.8	62.0	56.9	60.9
  45° Gloss	13.6	10.8	13.4	12.0	14.9	11.9
  MD = Machine Direction, TD = Transverse Direction, UT Str = Ultimate Tensile strength U. Elong = Ultimate Elongation
  ESCORENE ED7755.10 is a polyethylene polymer available from Exxon Chemical Company, Houston, Texas, having an I21 of 7.5, and MIR of 125, an Mw of 180,000, a density of 0.95 g/cc, produced using a dual reactor system.

  Example 9

  Several drums of granular samples (produced following the polymerization procedure above with a molar catalyst ratio (Catalyst A/Catlayst B) of 2.3 were tumble mixed with 1000 ppm Irganox™ 1076 and 1500 ppm Irgafos™ 1068 and 1500 ppm of calcium stearate. This tumble-mixed granluar resin was pelletized on a 2½″ (6.35 cm) Prodex compounding line at 400° F. (204° C.). Thus prepared pellets were film extruded on a 50 mm Alpine blown film line which is equipped with an extruder with 50 mm single screw (18:1 L/D ratio) and 100 mm annular die with 1 mm die gap. The extrusion conditions were: 400° F. (204° C.) die temperature, output rate—100 lb/hr (46 kg/hr). A typical set temperature profile was: 380° F./400° F./400° F./400° F./400° F./400° F./410° F./410° F. (193° C./204° C./204° C./204° C./204° C./204° C./210° C./210° C.) for Barrel1/Barrel2/Block adaptor/Bottom adaptor/Verical adaptor/Die bottom/Die middle/Die top. The pellet samples were extruded to produce 1.0 mil (25 μm) film sample at the line speed of 92 fpm (48 cm/sec) and 0.5 mil (13 μm) film sample at the line speed of 184 fpm (94 cm/sec) at the blow-up ratio (BUR) of 4.0. For both cases the bubble showed excellent stability with a typical “necked-in” wine glass shape. The FLH (frost line height) of blown bubble was maintained at 36 inches (91.4 cm) and 40 inches (101.6 cm), respectively for 1.0 mil (25 μm) and 0.5 mil (12.5 pm) film. The extrusion head pressure and motor load exhibited slightly higher than ESCORENE™ HD7755.10 (a conventional series reactor product of Exxon Chemical Company in Mt Belvue Tex.) at the same extrusion conditions. The resultant film properties are reported in Table B. All the film samples were conditioned at to 23° C., 50% humidity for 40 hours. Dart impact strength of 0.5 mil (12.5 μm) film exhibited 380 g, which exceeded that of ESCORENE™ HD7755.10 which showed 330 g.

  	TABLE B
  	Escorene ™ 7755	Polymer B
  I2 (g/10 min)	0.08		0.062
  I21 (g/10 min)	10		10.02
  I21/I2	134		160.5
  Density (g/cc)	0.952		0.9485
  Output (lb/hr) (kg/hr)	104		100
  	(47)		(47)
  Die rate (lb/hr/in die)	˜8		˜8
  Head pressure psi/MPa	7,200		7600
  	(50)		(53)
  Motor Load (amp)	56		61
  BUR	4		4
  FLH (inch) (cm)	36	40	36	40
  	(91.4)	(101.6)	(91.4)	(101.6)
  melt fracture	no		no	no
  Bubble	good		good	good
  Stability
  Take-up (fpm) (m/s)	92	185	92	184
  	(0.5)	(0.9)	(0.5)	(0.9)
  Film gauge (mil ) (μ)	1	0.5	1	0.5
  	(25)	(12.5)	(25)	(12.5)
  Dart Impact strength (g)	250	330	290	360
  Tensile str. (psi) (MPa)
  MD	8,400	11,300	8100	11400
  	(58)	(78)	(56)	(79)
  TD	7,900	10,400	7230	9520
  	(55)	(72)	(50)	(66)
  Elongation
  MD	350	230	410	330
  TD	570	390	580	410
  Elmendorf Tear (g/mil) (g/μ)
  MD	25	22	24	33
  	(0.98)	(0.87)	(0.95)	(1.30)
  TD	142	72	205	71
  	(5.59)	(2.83)	(8.07)	(2.80)
  Modulus (psi) (MPa)
  MD	127,000	144,000	131500	135350
  	(876)	(993)	(907)	(933)
  TD	146,000	169,000	160250	156300
  	(1007)	(1165)	(1105)	(1078)
  MD = machine direction, TD = transverse direction.

  Example 10

  Following the procedure of Example 9, several drums of granular samples (Polymer C produced following the polymerization procedure above with a molar catalyst ratio of Catalyst A to Catalyst B of 0.732 and Polymer D produced following the polymerization procedure above with a molar catalyst ratio of Catalyst A to Catalyst B or 2.6) were tumble mixed with 1000 ppm Irganox™ 1076, 1500 ppm of calcium stearate and 1500 ppm Irgafos™ 1068 then pelletized and extruded as described in Example 9. All films were conditioned at 23° C. and 50% humidity for 40 hours. Dart impact strength of a 0.5 mil (12.5 μm) film from both Polymer C and Polymer D exhibited 380 g, which exceeded that of ESCORENE™ HD 7755.10 which showed 330 g. The data are reported in Table C.

  TABLE C
  Sample	Polymer C	Polymer D	Escorene 7755
  Rxn Temp	85	85
  (° C.)
  C2 (psi) (kpa)	220	220
  	(1517)	(1517)
  H2/C2 (molar)	0.0014-0.0016	0.00102
  C6/C2 (molar)	0.0075-0.0078	0.00531-0.00586
  Mn	14,600	16,400
  Mw	309,100	298,200	291,500
  Mw/Mn	21.2	18.2	15.7
  HMW/LMW	53.8/46.2	50.5/49.5
  I2 (g/10 min)	0.056	0.049	0.08
  I21 (g/10 min)	6.48	6.7	10
  MFR (I21/I2)	115.8	138	134
  Density (g/cc)	0.9487	0.9461	0.952
  Output (lb/hr)	102	102	100
  (kg/hr)	(46)	(46)	(45)
  Die rate (lb/hr/	˜8	˜8	10
  in die)
  Head. (psi)	8,120	7,890	7,230
  (MPa)	(56)	(54)	(50)
  Motor Load	64.5	63	59
  (amp)
  BUR	4	4	4
  FLH (inch)	40	40	36	40	36	40
  (cm)	(101.6)	(101.6)	(91.4)	(101.6)	(91.4)	(101.6)
  melt fracture	no	no	no
  Bubble	Fair	Good	Good	Good	Good	Good
  Stability
  Film gauge	1	0.5	1	0.5	1	0.5
  (mil ) (μm)	(25.4)	(12.7)	(25.4)	(12.7)	(25.4)	(12.7)
  Dart Impact (g)	200	380	200	380	250	330
  Tensile
  strength
  MD (psi)	10,300	19,900	9,900	15,500	8,400	11,300
  (MPa)	(71)	(137)	(68)	(107)	(58)	(78)
  TD (psi)	7,900	13,800	8,400	14,500	7,900	10,400
  (MPa)	(55)	(95)	(58)	(100)	(55)	(72)
  Elongation (%)
  MD	320	240	290	250	350	230
  TD	630	385	610	350	570	390
  Elmendorf Tear
  MD (g/mil)	24	21	36	36	25	22
  (g/μ)	(0.95)	(0.83)	(1.42)	(1.42)	(0.98)	(0.87)
  TD (g/mil)	410	87	350	66	142	72
  (g/μ)	(16.1)	(3.4)	(13.8)	(2.6)	(5.6)	(2.8)
  Modulus
  MD (kpsi)	105	120	103	110	127	144
  (MPa)	(724)	(827)	(710)	(758)	(876)	(993)
  TD (psi)	128	126	129	114	146	169
  (MPa)	(883)	(869)	(889)	(786)	(1007)	(1165)
  Alpine line, 2″ screw, 4 inch (10.2 cm) die, 40 mil (1016 μm) die gap, 410° F. (210° C.) die set Temp.

  In addition to the examples above, other variations on polymerizing using the catalyst systems described herein include:

  • • 1. Compound I could be dissolved in a solvent, preferably toluene to form the desired weight % solution then used in combination with other catalyst systems.
    • 2. Catalyst A could be used as a 0.50 weight % solution in toluene and Catalyst B could be used as a 0.25 weight % solution in hexane at molar ratios of B to A of about 0.7 when the two are activated separately then mixed together (parallel activation) or at molar ratios of B to A of 2.2 to 1.5 when A is activated then B is added (sequential activation).
    • 3. Raising or lowering the reaction temperature to narrow or broaden the Mw/Mn, respectively.
    • 4. Changing residence time to affect product properties. Large changes can have significant impact. One to five, preferably four hours residence time appears to produce good product properties.
    • 5. Spraying the catalyst into the reactor in such a way as to create a particle lean zone. A particle lean zone can be created by a 50,000 lb/hr flow of cycle gas through 6 inch pipe. The catalyst can be atomized w/a spray nozzel using nitrogen atomizing gas.
    • 6. The activator, preferably MMAO 3A can be used at 7 weight % al in isopentane, hexane or heptane at feed rate sufficient to give an Al/Zr ratio of 100 to 300.
    • 7. Catalyst A is mixed on-line with MMAO 3A then Catalyst B is added on line, then the mixture is introduced into the reactor.
    • 8. Catalyst A is mixed on-line with MMAO 3A and Catalyst B is mixed on line with MMAO 3A thereafter the two activated catalysts are mixed on-line then introduced into the reactor.

  All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures. As is apparent form the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. It is within the scope of this invention to use two or more Group 15 containing metal compounds with one or more bulky ligand metallocene-type catalyst system and/or one or more conventional type catalyst system. Accordingly it is not intended that the invention be limited thereby.

Claims

1. A process for polymerizing olefin(s) comprising, combining said olefin(s), a catalyst composition having a first catalyst system component comprising a group 15 containing bidentate or tridentate ligated group 3 to 7 metal compound wherein the group 3 to 7 metal atom is bound to at least one leaving group and to at least two three group 15 atoms, and wherein at least one of the at least two of the group 15 atoms is bound to a group 15 or 16 atom are each bound to the third group 15 atom through a bridging group; and a second catalyst system component,

wherein said second catalyst component is a metallocene compound;

wherein said first catalyst component and said second catalyst component are added to a polymerization reactor in one of a solution, a suspension or an emulsion;

wherein the polymerization process is a continuous gas or slurry phase process, and

wherein the group 15 containing tridentate ligand group 3 to 7 metal compound is represented by the formula: ##STR00006##

wherein R⁸ to R¹² are each independently a methyl, ethyl, propyl, or butyl group.

2. The process of claim 1 wherein the second catalyst system comprises a bulky ligand metallocene compound, a conventional transition metal catalyst selected from the group consisting of Ziegler-Natta catalysts, vanadium containing catalysts, and Phillips catalysts, or combinations thereof.

3. The process of claim 1 wherein the metal in the group 15 containing metal compound is a group 4 to 6 metal.

4. The process of claim 1 wherein the bridging group is selected from the group consisting of a C₁ to C₂₀ hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, and phosphorus.

5. The process of claim 1 wherein the group 15 or 16 atom may also be bound to nothing, a hydrogen, a group 14 atom containing group, a halogen, or a heteroatom containing group, and wherein each of the two group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom, a hydrocarbyl group, or a heteroatom containing group.

6. The process of claim 1 wherein the group 15 containing metal compound is represented by the formula: ##STR00007##

7. The process of claim 6 wherein R⁴ and R⁵ are represented by the formula ##STR00008##

8. The process of claim 7 wherein R⁹, R¹⁰ and R¹² are independendy a methyl, ethyl, propyl or butyl group.

9. The process of claim 8 wherein R⁹, R¹⁰ and R¹² are methyl groups, and R⁸ and R¹¹ are hydrogen.

10. The process of claim 9 wherein M is a group 4 metal L, Y, and Z are nitrogen, R¹ and R² are a hydrocarbon radical, R³ is hydrogen, and R⁶ and R⁷ are absent.

11. The process of claim 9 wherein M is a group 4 metal, L and Z are nitrogen, L′ is a hydrocarbyl radical, and R⁶ and R⁷ are absent.

12. The process of claim 2 1 wherein the second catalyst system component comprises a bulky ligand metallocene compound of the general formula L^DMQ₂(YZ)X_n

L^AL^BMQ_n or L^AAL^BMQ_n

wherein M is a group 3 to 16 metal 4, 5 or 6 metal atom,

L^D is a bulky ligand that is bonded to M,

L^A and L^B are selected from the group consisting of cyclopentadienyl, tetrahydroindenyl, indenyl, fluorenyl, and substituted versions thereof, L^A and L^B are each bonded to M;

Q is a univalent anionic ligand bonded to M monoanionic leaving group,

Q₂(YZ) forms a unicharged polydentate ligand,

X is a univalent anionic group or a divalent anionic group, and

n is 1 or 2

A is a divalent bridging group containing at least one group 13 to group 16 atom; and

n is 0, 1 or 2.

13. The process of claim 12 wherein X is a carbamate, carboxylate, or other heteroallyl moiety described by the unicharged polydentate ligand Q₂(YZ).

14. The process of claim 12 wherein M is a group 4 to 6 metal.

15. The process of claim 12 wherein M is a group 4 metal and L^D is an indenyl group or a fluorenyl group .

16. The process of claim 1 wherein the second catalyst system comprises a conventional transition metal catalyst selected from the group consisting of Ziegler-Natta catalysts, vanadium containing catalysts, Phillips catalysts and combinations thereof.

17. The process of claim 1 wherein the catalyst systems comprise composition further comprises an activator.

18. The process of claim 1 wherein the polymerization process is a continuous gas or slurry phase process.

19. The process of claim 1 wherein the olefin(s) are ethylene and one or more other olefin(s).

20. The process of claim 2 wherein the group 15 containing bidentate or tridentate ligated group 3 to 7 metal compound and the bulky ligand metallocene compound 1 wherein said first catalyst component and said second catalyst component are present in a molar ratio of 1:99 to 99:1.

21. The process of claim 2 wherein the group 15 containing bidentate or tridentate ligated group 3 to 7 metal compound and the bulky ligand metallocene compound 1 wherein said first catalyst component and said second catalyst component are present in a molar ratio of 20:80 to 80:20.