KR100486991B1 - Mixed transition metal catalyst systems for olefin polymerization - Google Patents

Abstract

The invention is suitable for mixing olefin monomers comprising one late transition metal catalyst system and one or more different catalyst systems selected from the group consisting of late transition metal catalyst systems, transition metal metallocene catalyst systems and Ziegler-Natta catalyst systems. A transition metal olefin polymerization catalyst system. Preferred embodiments include one or more late transition metal catalyst systems comprising a Group 9, 10 or 11 metal complex stabilized by a bidentate ligand structure, and a Group 4 metal complex stabilized by one or more auxiliary cyclopentadienyl ligands. One or more transition metal metallocene catalyst systems. Polymerization processes for olefin monomers include contacting one or more olefins with these catalyst systems under polymerization conditions.

Description

Mixed transition metal catalyst system for olefin polymerization {MIXED TRANSITION METAL CATALYST SYSTEMS FOR OLEFIN POLYMERIZATION}

The present invention relates to a mixed transition metal catalyst system comprising a late transition metal catalyst compound and a metallocene compound and to olefin polymerization using the same.

Early transition metal catalysts for olefin polymers by coordination polymerization are well known, and typically they are typical Ziegler type catalysts based on Groups 4 and 5 of the Periodic Table (new nomenclature of IUPAC), and newer metals based on Groups 4-6 metals. Rosene catalyst. However, certain late transition metal catalysts suitable for olefin polymerization did not provide the same level of activity or molecular weight capacity for olefin polymerization during the development of these catalyst systems, and further studies have been published to address these shortcomings.

Johnson, Killian and Brookhart, J. Am. Chem. Soc., 1995, 117, 6414, reporters disclose the use of Ni and Pd complexes for the solution homopolymerization of ethylene, propylene and 1-hexene. The catalyst precursor is a planar square, M ²⁺ , d ⁸ , 16 electron complex incorporating a substituted bidentate diimine ligand. The active coordination site is filled with methyl or bromide ligands. Methyl ligand complexes are _{^{H + (OEt 2) 2 [}} B (3,5- (CF 3) 2 C 6 H 3) 4] - are activated by, bromide ligand complexes as cocatalyst methyl alumoxane (MAO) or Activated with diethylaluminum chloride.

EP-A2-0 454 231 states that Group 8b metal catalysts are suitable for the polymerization of ethylene, α-olefins, diolefins, functionalized olefins and alkynes. The disclosed catalyst precursor is a Group 8b metal (Group 8, 9, 10, new nomenclature of IUPAC) compounds that are subsequently activated by compounds comprising individual borate anions. Ethylene homopolymerization in a solution of methylene chloride, toluene and diethyl ether is illustrated.

Since the new late transition metal catalysts exhibit different characteristics than the transition metal metallocene catalysts or the typical Ziegler-Natta catalysts when used in olefin polymerizations, the mixing effect of these catalysts to determine useful advantages is very interesting.

Summary of the Invention

The present invention provides a mixed transition suitable for polymerization of an olefin monomer comprising one late transition metal catalyst system and at least one different catalyst system selected from the group consisting of a late transition metal catalyst system, a transition metal metallocene catalyst system and a typical Ziegler catalyst system. A metal olefin polymerization catalyst system. Preferred embodiments include at least two late transition metal catalyst systems, including at least one late transition metal catalyst system, and at least one auxiliary cyclopentadie, comprising a Group 9, Group 10 or Group 11 metal complex stabilized by a bidentate ligand structure. One or more transition metal metallocene catalyst systems comprising a Group 4 metal complex stabilized by a Neil ligand, or one or more later transition metal catalyst systems as disclosed, and homogeneous vanadium catalysts and heterogeneous TiCl ₃ / MgCl ₂ donor catalyst systems A mixture of one or more Ziegler-Natta catalyst systems selected from the group consisting of: Olefin monomer polymerization processes include contacting one or more olefins with these catalyst systems under polymerization conditions.

1 and 2 show composition distribution (CD) traces by temperature increasing elution fraction (“TREF”) as disclosed in polymer samples P2-2 through P2-3 of US Pat. No. 5,008,204, respectively.

The later metal catalyst system of the present invention may be derived from the late transition metal compound of Formula 1:

LMX _r

Where

M is a 9, 10 or 11 metal, preferably a d ⁶ , d ⁸ or d ¹⁰ metal, most preferably a d ⁸ metal,

L is a bidentate ligand that stabilizes the planar square structure and balances the charge of the oxidation state of MX _r ,

Each X is independently a hydride radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, a halocarbyl radical, a substituted halocarbyl radical and a hydrocarbyl- and halocarbyl-substituted organometaloid radical, or two X are Linked to and bonded to a metal atom to form a metallocycle ring containing from about 3 to about 20 carbon atoms, or at least one X may be a neutral hydrocarbyl containing a donor ligand, for example olefins, diolefins or Can be an arine ligand,

r is 0, 1, 2 or 3.

Using a Lewis acid activator, such as methylalumoxane, aluminum alkyl or alkylaluminum halide, which can provide the X ligand to the transition metal component as disclosed above, or if the ion activator can extract X The above X may further be independently selected from halogen, alkoxide, aryloxide, amide, phosphide or other monovalent anionic ligand (two such X may combine to form an anion chelating ligand), or May be one or more neutral non-hydrocarbyl atom containing donor ligands such as phosphines, amines, nitriles or CO ligands

In a preferred embodiment of the invention, the bidentate ligand L is defined by the formula

Where

A is a crosslinking group containing a group 13 to 15 element,

E are each independently a group 15 or 16 element bonded to M,

Each R is independently a C ₁ -C ₃₀ containing radical or diradical, which is hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometallic, halocarbyl-substituted Organometalloid,

m and n are independently 1 or 2, depending on the valence of E,

p is the charge on the bidentate ligand in which the oxidation state of MX _r is satisfied.

In the most preferred embodiment of the invention the bridging group, A, is defined by the general formula:

Where

G is a Group 14 atom, in particular C, Si and Ge,

Q is a Group 13 atom, in particular B and Al,

R 'is independently a hydride radical, a C ₁ -C ₃₀ hydrocarbyl radical, a substituted hydrocarbyl radical, a halocarbyl radical, a substituted halocarbyl radical and a hydrocarbyl- and halocarbyl-substituted organometaloid radical, Optionally two or more adjacent R ′ form one or more C ₄ -C ₄₀ rings to produce saturated or unsaturated cyclic or polycyclic rings.

Also in the most preferred embodiment of the invention, each R is a bulky C ₁ -C ₃₀ containing radical group, which is hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted halocarbyl, substituted organometalloid, Hydrocarbyl-substituted organometallics, halocarbyl-substituted organometallics. Bulky radical groups are bound to E by phenyl, substituted phenyl, alkyl and substituted alkyl, especially those bound to E by tertiary carbon atoms, and by alicyclic and polyalicyclic containing hydrocarbyls, especially tertiary carbon, etc. Are things.

In the above definition, the term “substituted” is as defined, or is a C ₁ -C ₃₀ containing radical group, which is essentially hydrocarbyl, but instead of one or more carbon atoms, one or more non-hydrocarbyl elements (eg, Si, Ge, O, S, N, P, halogen, etc.) may be included.

In the most preferred embodiment of the invention, M is a Group 10 metal, E is a Group 15 atom, in particular nitrogen, m and n are 1 and p is 0, the crosslinking is shown as A-1 and R is substituted Phenyl group, preferably R 'group at the 2 and 6 positions. For high molecular weight polymers, R 'at the 2 and 6 positions are preferably C ₃ -C ₃₀ hydrocarbyl groups in which secondary or tertiary carbon atoms are bonded to the phenyl group. For low molecular weight polymers, R in the 2 and 6 positions is preferably a C ₁ -C ₂ hydrocarbyl group or a C ₃ -C ₁₀ hydrocarbyl group in which the primary carbon atom is bonded to a phenyl group. For macromer preparation, R in the 2 and 6 positions is a hydride.

Transition metal metallocene catalyst systems comprising Group 4 metal complexes stabilized by one or more auxiliary cyclopentadienyl ligands according to the present invention are known in the art as metallocene catalysts. The term includes a compound containing a single cyclopentadienyl ligand or a substituted derivative thereof ("monocyclopentadienyl metallocene") and two cyclopentadienyl ligands or a substituted and unsubstituted derivative thereof ("biscyclo Pentadienyl metallocene "). Each group may not be crosslinked, or may be crosslinked between two cyclopentadienyl ligands or between a single cyclopentadienyl ligand and a heteroatom ligand, for example, on the same transition metal center. Precursor compounds and the catalyst system itself are well known in the art.

Further descriptions of metallocene compounds can be found in the patent literature, for example in US Pat. Nos. 4,871,705, 4,937,299, 5,324,800, EP-A-0 418 044, EP-A-0 591 756, WO -A-92 / 00333 and WO-A-94 / 01471. The metallocene compounds of the invention are those disclosed as mono- or bis-substituted Group 4, 5, 6, 9 or 10 transition metal compounds, wherein the cyclopentadienyl substituents may themselves be substituted with one or more groups It may be crosslinked to each other, or may be crosslinked via heteroatoms to the transition metal. Preferably, for high molecular weight polymer components, the biscyclopentadienyl (or substituted biscyclopentadienyl, such as indenyl or substituted indenyl) rings will be crosslinked and lower alkyl-substituted at the 2 position And (C ₁ -C ₆ ) and will further include alkyl, cycloalkyl, aryl, alkaryl and / or arylalkyl substituents, the latter being for example multiple of US Pat. Nos. 5,278,264 and 5,304,614 Condensed or pendant ring structures, including ring structures. These substituents each have inherently hydrocarbyl properties and will typically have less than 30 carbon atoms, but heteroatoms containing 1 to 3 non-hydrogen / carbon atoms, for example N, S, O, P , Si or Ge.

Metallocene compounds suitable for the preparation of linear polyethylene or ethylene-containing copolymers, which mean that the copolymer comprises at least two different monomers, may be essentially any known in the art and are listed in the specific list. See WO-A-92 / 00333 and US Pat. Nos. 5,001,205, 5,057,475, 5,198,401, 5,304,614, 5,308,816 and 5,324,800. The selection of metallocene compounds used to prepare isotactic or syndiotactic polypropylene blends, and the synthesis thereof, are well known in the art, the specific references may be both patent and academic literature, See, eg, Journal of Organmetallic Chemistry, 369, 359-370 (1989). Typically these catalysts are stereoregular asymmetric chiral or crosslinked chiral metallocenes. For example, US Pat. No. 4,892,851, US Pat. No. 5,017,714, US Pat. No. 5,296,434, US Pat. No. 5,278,264, WO-A- (PCT / US92 / 10066), WO-A-93 / 19103, EP-A2-0 577 581, EP-A1-0 578 838, and in the academic literature ["The Influence of Aromatic Substituents on the Polymerization Behavior of Bridged Zirconocene Catalyst", Spaleck, W., et al. , Organometallics 1994, 13, 954-963 and "ansa-Zirconocene Polymerization Catalysts with Annealated Ring Ligands-Effects on Catalytic Activity and Polymer Chain Lengths", Brinzinger, H., et al, Organometallics 1994, 13, 964-970] And their references.

Preferably the monocyclopentadienyl metallocene catalyst component additionally comprises group 15 or 16 heteroatoms covalently bonded to both ring carbons of the cyclopentadienyl group-containing ligand via a Group 4 transition metal center and a bridging group to be. Such catalysts are known in the art and are known, for example, in US Pat. Nos. 5,055,438, 5,096,867, 5,264,505, 5,408,017, 5,504,169 and WO 92/00333. See also US Pat. Nos. 5,374,696, 5,470,993 and 5,494,874 and International Patents WO 93/19104 and EP 0 514 828A. For cyclic olefin containing copolymers, WO-94 / 17113, co-pending US patent 08 / 412,507 (filed March 29, 1995) and co-pending US patent no. 08 / 487,255 (6, 1995) May 7) and those published in WO96 / 002444. In addition, the non-crosslinked monocyclopentadienyl, heteroatom-containing Group 4 transition metal catalyst component of co-pending US patent application Ser. No. 08 / 545,973, filed Sep. 25, 1995, will be suitable for the present invention. . The aforementioned documents are each incorporated by reference in accordance with US patent practice.

Non-limiting representative metallocene compounds include mono-cyclopentadienyl compounds, such as pentamethylcyclopentadienyl titanium tri (isopropoxide), pentamethylcyclopentadienyltribenzyl titanium, dimethylsilyltetramethylcyclo Pentadienyl tert-butylamido titanium dichloride, pentamethylcyclopentadienyl titanium trimethyl, dimethylsilyltetramethylcyclopentadienyl tert-butylamido zirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl- Cyclododecylamido hafnium dihydride, dimethylsilyltetramethylcyclopentadienyl-dodecylamido titanium dimethyl, uncrosslinked biscyclopentadienyl compounds such as bis (1,3-butyl, methylcyclopenta Dienyl) zirconium dimethyl, pentamethylcyclopentadienyl-cyclopentadienyl zirconium dimethyl; Crosslinked biscyclopentadienyl compounds such as dimethylsilylbis (tetrahydroindenyl) zirconium dichloride dimethylsilylbisindenyl zirconium dichloride, dimethylsilylbisindenyl hafnium dimethyl, dimethylsilylbis (2-methylbenzide Nil) zirconium dichloride, dimethylsilylbis (2-methylbenzindenyl) zirconium dimethyl; And further mono-, bis- and triscyclopentadienyl compounds, such as those disclosed in US Pat. Nos. 5,324,800 and EP-A-0 591 756.

Typical Ziegler-Natta transition metal catalyst systems (“Z-N” systems) typically include Group 4, 5 or 6 transition metal halides or oxyhalides, Ziegler promoters and optional donor molecules. These catalyst systems are known and can be used according to the invention. The disclosures of US Pat. Nos. 4,701,432 and 4,987,200 include suitable disclosures of catalytic compounds useful in the present invention. Both are incorporated by reference in accordance with US patent practice. In particular, reference may be made to columns 5, 27 to 5, 6, 5 and 4,987,200 of columns 27, 22 to 28, 17 of column 4,701,432. Preferred catalysts of the present invention for elastomeric polymers are those of US Pat. No. 4,987,200. In the case of polyethylene and isotactic polypropylene, typically known catalyst systems suitable for both homo- and copolymers will be suitable for the present invention.

Those skilled in the art should be aware that other catalyst systems can also be used as components of the mixed catalyst system of the present invention. Examples include the disclosures of US Pat. Nos. 5,079,205, 5,318,935, and 5,504,049, each of which is incorporated by reference in accordance with US patent practice.

In theory any ratio of catalyst system to remainder can be used. Preferred ratios based on moles of transition metal are 200: 1 to 1: 1. By transition metal is meant here two different classes of the group of catalysts of the invention. When using two or more catalyst systems, the preferred ratio between any two is as disclosed. It is known in the art that in setting the ratio it is important to select the ratio taking into account the difference in the polymerization activity of the selected system under the selected conditions. For example, the presence of α-olefins will inhibit the activity of the late transition metal catalyst system compared to the metallocene system. Thus, if only a small amount of one polymer component is desired, a ratio of at least 200: 1 would be preferred.

In this patent specification, the term “procatalyst or activator” is any compound or component that can be used interchangeably and that can activate later transition metal compounds, metallocene compounds and ZN catalysts or when they are activated separately It may be any independent.

The late transition metal compounds, metallocene compounds and Z-N catalysts according to the invention can be activated for polymerization catalysis in any manner sufficient to permit coordination polymerization. This can be done, for example, if each can be similarly extracted to substitute one ligand which can be extracted from an olefinically unsaturated monomer and another ligand which can be inserted or can be inserted. Typical activators in the field of metallocene polymerization are suitable activators; Typically Lewis acids, such as alumoxane compounds, and ionized, anionic precursor compounds that extract one ligand and provide a compatible non-coordinated anion of opposite charge so as to ionize the transition metal center with cations. In addition, typical organometallic compound Ziegler cocatalysts can be used as late transition metal catalysts and typical Ziegler catalysts themselves.

When using a mixed catalyst system, the choice of catalyst activator or activators depends on the combination of transition metal compound used. Late transition metal compounds can be activated using alumoxanes, Ziegler cocatalysts, "non-coordinating anion" precursor compounds and halide salts of Group 13-16 metals, each of which is described in more detail below. The transition metal metallocene compound is preferably activated using an alumoxane or "non coordinating anion" precursor compound. Although most Ziegler promoters can be used with most transition metal metallocene compounds, they are typically poor activators. Halide salts of Group 13-16 metals should not be used with transition metal metallocene compounds. Typical Ziegler-Natta catalysts are preferably activated by a Ziegler promoter. The presence of alumoxane or "uncoordinated anion" precursor compounds does not present any problems, but the presence of halide salts of Group 13-16 metals is undesirable. In the most preferred embodiment of the present invention, when the mixed catalyst system comprises two or more different late transition metal compounds, any of the activator combinations listed above can be used. If the mixed catalyst system comprises at least one late transition metal compound and at least one transition metal metallocene compound, the preferred activator system is a "non-coordinated anion" precursor compound or alumoxane or mixtures thereof, with alumoxane being more desirable. If the mixed catalyst system comprises at least one late transition metal compound and at least one typical Ziegler-Natta catalyst, the most preferred activator is a Ziegler-cocatalyst.

Ziegler promoters are typically organometallic compounds of Group 1, 2, 12 or 13 metals of the Periodic Table of Elements. Preference is given to organoaluminum compounds selected from the group consisting of aluminum alkyls, aluminum alkyl halides and aluminum halides. They are of the formula Al (R ¹ ) _s X ′ _3-s , wherein R ¹ is independently a hydride or C ₁ to C ₁₀ hydrocarbyl comprising an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, X 'is halogen s is an integer from 0 to 3) and Al ₂ R ¹ ₃ X ' ₃ (which is a hydrocarbylaluminum sesquihalide).

Examples are triethylaluminum, triisobutylaluminum, diethylaluminum chloride, Al ₂ Et ₃ Cl ₃ and Al ₂ (i-Bu) ₃ Cl ₃ . As generally recognized in the art, these Ziegler promoter compounds do not effectively activate metallocene compounds.

In an unsupported catalyst system in which the activator is a Ziegler promoter, the molar ratio of the preferred late transition metal compound to the Ziegler promoter (typically measured in moles of aluminum) is from about 1: 1000 to 1: 1, more preferably about 1 : 200 to 1: 1, most preferably about 1: 100 to 1: 1, higher or lower ratios may also be used. The preferred molar ratio of the Ziegler-Natta catalyst (based on moles of transition metal atoms) to the Ziegler cocatalyst (typically measured in moles of aluminum) is preferably from about 1: 10000 to 1:10, more preferably about 1 : 5000 to 1:10, most preferably about 1: 2000 to 1:10, and higher or lower ratios may also be used. The preferred molar ratio of total transition metal compound to Ziegler cocatalyst is preferably from about 1: 10000 to 1: 1, more preferably from about 1: 5000 to 1: 1, most preferably from about 1: 2000 to 1: 1. And higher or lower ratios may also be used. The total transition metal compound is measured as the total moles of transition metal atoms present in the mixed catalyst system.

Alkylalumoxanes and modified alkylalumoxanes are suitable catalyst activators for all types of catalyst systems of the present invention. Alumoxane components useful as catalyst activators are typically oligomeric aluminum represented by the general formula (R ² -Al-O) _n which is a cyclic compound or general formula R ² (R ² -Al-O) _n AlR ² _{2 which} is a linear compound. Compound. In general alumoxane R ² is independently a C ₁ to C ₁₀ hydrocarbyl radical, for example methyl, ethyl, propyl, butyl or pentyl, and “n” is an integer from 1 to about 100. R ² may also independently be halogen, including fluorine, chlorine and iodine, and other non-hydrocarbyl monovalent ligands such as amides, alkoxides, etc., provided that up to 25 mole% of R ² is Non-hydrocarbyl. Most preferably R ² is methyl and "n" is at least 4. Alumoxane can be prepared by a variety of methods known in the art. For example, aluminum alkyl may be treated with water dissolved in an inert organic solvent or may be contacted with a hydrated salt such as hydrated copper sulfate suspended in an inert organic solvent to produce alumoxane. In general, however, in production, the reaction of aluminum alkyl with a limited amount of water produces a mixture of linear and cyclic species of alumoxane. Preference is given to methylalumoxanes and modified methylalumoxanes. For more detailed description, for example, U.S. Patent Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476A1, EP 0 279 586 131, EP 0 516 476 A, EP 0 594 218 A1 And WO 94/10180, each of which is incorporated by reference in accordance with US patent practice.

In unsupported catalyst systems where the activator is alumoxane, the preferred molar ratio of total transition metal compound to activator is from 1: 10000 to 10: 1, more preferably from about 1: 5000 to 10: 1, even more preferably from about 1: 1000 and 1: 1.

The term "non-coordinating anion" as used for ionizing, anionic precursor compound ("non-coordinating anion precursor") is an anion that is easy to be substituted by a neutral Lewis base either by coordinating the transition metal cation or by coordinating it weakly. Means. "Compatible" noncoordinating anions are those that do not degrade to neutrality when the complex initially formed between the transition metal catalyst compound and the ionization, anion precursor compound is degraded. In addition, the anion will not transfer anionic substituents or fragments to the cations to form neutral quaternary metal compounds and neutral by-products from the anion. Non-coordinating anions useful according to the present invention are those that are compatible and can be easily substituted with olefin unsaturated monomers during polymerization while stabilizing the late transition metal cation or transition metal metallocene catalyst in terms of compatibility and balancing their ionic charge. In addition, the anions useful in the present invention should have sufficient molecular weight size to assist in partially preventing or preventing the neutralization of late transition metal cations by Lewis bases which are not polymerization monomers which may be present in the polymerization process.

The disclosure of ion catalysts comprising transition metal cations and non-coordinating anions suitable for coordination polymerization is described in U.S. Patents 5,064,802, 5,132,380, 5,198,401, 5,278,119, 5,321,106, 5,347,024, 5,408,017, It is shown in the initial studies of WO 92/00333 and WO 93/14132. They disclose a preferred method of preparation in which the metallocene is protonated by an anion precursor so that the alkyl / hydride groups are extracted from the transition metal to be charge balanced by cationic and non-coordinating anions. These disclosures are useful to those skilled in the art for the later transition metal catalysts of the present invention.

It is also known to use ionizing ionic compounds which do not contain active protons and are capable of producing both active metal cations and uncoordinated anions. See EP-A-0 426 637, EP-A-0 573 403 and US Pat. No. 5,387,568. Reactive cations which are not Bronsted acids include ferricium, silver, trophylium, triphenylcarbenium and triethylsilyllium, or alkali metal or alkaline earth metal cations such as sodium, magnesium or lithium cations. Another group of noncoordinating anion precursors suitable in accordance with the present invention are hydrated salts comprising alkali metal or alkaline earth metal cations and noncoordinating anions as disclosed above. The hydrated salts are commercially or readily synthesized LiB (pfp) ₄ , for example (pfp) is pentafluorophenyl or perfluorophenyl, by reaction of a metal cation-non-coordinating anion salt with water. Can be prepared by hydrolyzing to produce [Li.xH ₂ O] [B ([pfp) ₄ ].

Preferably any metal or metalloid capable of forming a coordination complex that is resistant to degradation by water (or other Bronsted or Lewis acids) may be used or contained in the anion. Suitable metals include, but are not limited to, aluminum, gold, platinum, and the like. Suitable metalloids include, but are not limited to, boron, phosphorus, silicon, and the like. The disclosure of the non-coordinating anions and precursors of the aforementioned documents is incorporated by reference in accordance with US patent practice.

A further method of preparing an ionic catalyst is a late transition metal compound or transition metal metal which initially acts as a neutral Lewis acid but acts to extract hydrocarbyl, hydride or silyl ligands to produce transition metal cations and stabilized uncoordinated anions. Non-coordinated anion precursors are used which form cations and anions upon ionization reactions with a Rosene catalyst compound, for example tris (pentafluorophenyl) borone. Reference may be made to EP-A-0 427 697 and EP-A-0 520 732 for metallocene catalyst systems. Ion catalysts for coordination polymerization can also be prepared by oxidizing the metal center of the transition metal compound by an anion precursor containing a metal oxidizing group together with an anionic group, see EP-A-0 495 375. The disclosure of non-coordinating anions and precursors thereof in these documents is similarly incorporated by reference in accordance with US patent practice.

The proton portion of the ionic non-coordinating anion precursor promoter may be a Bronsted acid, such as a proton or protonated Lewis acid, or a reducing Lewis acid, such as perisenium or silver cation, or an alkali or alkaline earth metal cation. , For example sodium, magnesium or lithium cations, the total transition metal to activator molar ratio may be any ratio, but is preferably from about 10: 1 to 1:10, more preferably from about 5: 1 to 1: 5, even more preferably about 2: 1 to 1: 2, and most preferably about 1.2: 1 to 1: 1.2, with a ratio of about 1: 1 being most preferred. Similar ratios may be used for other noncoordinating anion precursor compounds.

Late transition metal catalyst compounds of the invention may also 13 to 16-group metal or a halide salt of the metalloid and preferably the fluoride and oxyfluoride salts, e.g., _{^{BF 4 -, PF 6 -,}} SbF 6 -, TeOF 6 ^- and AsF ₆ ^- may be activated using an ionizing anion precursors including those that provide the anions. However, such activators should preferably be avoided when the mixed catalyst system is activated together in situ, since the metallocene compound is sensitive to an insufficient volume of anions to provide compatibility.

When a halide salt of a Group 13-16 metal or metalloid is used as the activator, the preferred total transition metal compound to activator molar ratio is preferably 10: 1 to 1:10, more preferably about 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2, even more preferably 1.2: 1 to 1: 1.2, with 1: 1 being most preferred. Higher or lower ratios may also be used.

The late transition metal catalyst system of the present invention may further be prepared by mixing any order of the bidentate ligand L, or known precursor thereof, with a suitable late transition metal complex and activator compound. For example, the bidentate ligand L precursor (2,6-i-Pr ₂ C ₆ H ₃ N = CH) ₂ is a late transition metal complex NiBr in a solvent such as toluene in which an activator compound methylalumoxane is dissolved. ₂ - may be added to the (MeOCH ₂ CH ₂ OMe). Optionally, an oxidizing or reducing agent can additionally be used to obtain the desired d ⁶ , d ⁸ or d ¹⁰ metal compound. All reactants may be added in any order or even essentially simultaneously. This activated catalyst can be mixed with the individually activated metallocene complex or with the metallocene compound to be subsequently activated.

When used in mixed catalyst system ion catalysts comprising metallocene cations and uncoordinated anions, the total catalyst system may further comprise one or more scavenging compounds. The term "erasing compound" includes compounds effective for removing polar impurities from the reaction environment. Impurities can be inadvertently introduced into any polymerization reaction component, especially in solvents, monomers, and catalyst feeds and adversely affect catalyst activity and stability. Impurities can reduce, change or even remove catalyst activity. Polar impurities or catalyst poisons include water, oxygen, metal impurities and the like. Since the later transition metal catalysts of the present invention may be less sensitive to impurities than metallocene catalyst systems, the reduction or removal of poisons is a desirable purpose, particularly when using these mixed catalysts. In order to avoid the addition of such impurities to the reaction vessel, preferred steps are taken, for example by chemical treatment or careful separation techniques, after or during the synthesis or preparation of the various components. Some small amounts of scavenging compound may still be used in the polymerization process itself, but will be minimized to avoid deactivation of the metallocene component.

Typically the scavenging compound is an organometal compound, for example US Pat. Nos. 5,153,157, 5,241,025 and WO-A-91 / 09882, WO-A-94 / 03506, WO-A-93 / 1413 and Group 13 organometallic compounds of WO 95/07941. Exemplary compounds include triethyl aluminum, triethyl borane, triisobutyl aluminum, methylalumoxane, isobutyl alumoxane and n-octyl aluminum. These scavenging compounds having bulky or C ₈ -C ₂₀ linear hydrocarbyl substituents covalently bonded to the metal or metalloid center are preferred to minimize side effects with the active catalyst. If alumoxane or Ziegler promoter is used as activator, any excess relative to the amount of transition metal compound present will act as the scavenger compound and no additional scavenger compound may be required. The amount of scavenger used with the transition metal cation-uncoordinated anion pair is minimized during the polymerization reaction in an amount effective to increase activity.

Chain transfer or modifier components may also be added to the mixed catalyst system. Suitable chain transfer agents for reducing the molecular weight of polymers prepared from transition metal metallocenes or Ziegler-Natta catalyst systems are hydrogen and the general formula H _4-x SiR ^* _{x where} x is 1, 2 or 3 and R is independent C ₁ -C ₂₀ hydrocarbyl or hydrocarbyloxy radical, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, decyl, dodecyl, phenyl, methoxy, ethoxy, propoxy, Compounds such as silane of phenoxy and the like, but not limited to these. When alumoxane or Ziegler cocatalyst is used as the activator component, alcohols such as ethanol, isopropanol or phenol, and boranes such as catechol borane can be used as chain transfer agent. The disclosed chain transfer agents do not effectively reduce the molecular weight of polymers made from late transition metal catalyst systems.

The passivated catalyst system of the present invention will be useful in heteropolymerization processes such as bulky, slurry and gas phase polymerizations. They can be prepared by any effective method that supports other coordination catalyst systems, and effective means that the catalyst so prepared can be used to prepare the polymer in the chosen heteropolymerization process. Preferred methods include co-pending US patent application Ser. No. 60/020095, filed June 17, 1996, co-pending US patent application Ser. No. 08 / 466,547, filed June 6, 1995, and its counterpart And those mentioned in US Patent Application No. 08 / 474,948, filed June 7, 1995 and published as WO 96/04319. Activated catalysts can also be supported according to WO 91/0882 and WO 94/03506, especially when using ionization activators that provide electronically stabilized uncoordinated anions. All literature is incorporated in accordance with US patent practice.

Additional methods are shown in the following disclosures for metallocene catalysts, which will also be suitable for the catalyst system of the present invention. U. S. Patent No. 4,937, 217 discloses a mixture of trimethylaluminum and triethylaluminum, which is generally added to non-dehydrated silica, with the addition of a metallocene catalyst component. EP-308177-B1 generally discloses the addition of wet monomers to a reactor containing metallocene, trialkylaluminum and non-dehydrated silica. US Pat. Nos. 4,912,075, 4,935,397 and 4,937,301 generally relate to adding trimethylaluminum to non-dehydrated silica followed by the addition of metallocene to form a dry supported catalyst system. US Pat. No. 4,914,253 discloses the production of polyethylene wax by adding trimethylaluminum to non-dehydrated silica and adding metallocene and then drying the resulting supported catalyst system with a certain amount of hydrogen. US Pat. Nos. 5,008,228, 5,086,025 and 5,147,949 generally add trimethylaluminum to water immersed silica to form alumoxane in situ and then form metallocene to form a dry supported catalyst system. It starts. U.S. Patent Nos. 4,808,561, 4,897,455 and 4,701,432 disclose techniques for forming supported catalysts, wherein inert carriers, typically silica, are calcined and contacted with metallocene (s) and activator / promoter components do. US 5,238,892 discloses mixing a metallocene with alkyl aluminum followed by addition of non-dehydrated silica to form a dry supported catalyst system. US Pat. No. 5,240,894 generally describes supported metallocene / alumoxane catalyst systems by forming a metallocene / alumoxane reaction solution, adding a porous carrier, and evaporating the resulting slurry to remove residual solvent from the carrier. It is about forming. All literature is incorporated in accordance with US patent practice.

Polymeric carriers will also be suitable for the present invention, see for example WO 95/15815 and US Pat. No. 5,427,991. As disclosed for these metallocene catalysts in these documents, the catalyst complexes of the present invention are either chemically adsorbed or absorbed on a polymeric support, in particular a support made of porous material, or chemically via functional groups covalently attached to the polymer chain. Are combined.

When the activator is alumoxane For the immobilized catalyst system of the present invention, the preferred total transition metal compound to activator molar ratio is from 1: 500 to 10: 1, more preferably from about 1: 200 to 10: 1, even more Preferably 1: 120 to 1: 1.

Suitable solid particle supports are typically polymerizable or refractive oxide materials, each of which is preferably porous. Any support material, preferably a porous support material such as talc, an inorganic oxide such as silica, alumina, an inorganic chloride such as magnesium chloride and a resinous support material such as polystyrene polyolefin or a polymerizable compound Or any other organic support material or the like has an average particle size of at least 10 μm. Preferred support materials are inorganic oxide materials, which include Group 2, 3, 4, 5, 13 or 14 metal or metalloid oxides of the Periodic Table of Elements. In a preferred embodiment, the catalyst support material comprises silica, alumina, silica-alumina and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica, alumina or silica-alumina are magnesia, titania, zirconia and the like.

In a preferred embodiment of the process of the invention, a mixed catalyst system is used in the liquid phase (solution, slurry, suspension, bulk phase or combinations thereof), in a high pressure liquid or supercritical fluid phase or in the gas phase. Each of these methods can be used in a single, parallel or series reactor. The liquid process comprises contacting the above disclosed catalyst system in an appropriate diluent or solvent with an olefinically unsaturated monomer and reacting the monomer for a sufficient time to produce the copolymer of the present invention. Hydrocarbyl solvents are suitable and both aliphatic and aromatic are preferred, hexane and toluene. Bulk and slurry processes are typically carried out by contacting the catalyst with a liquid monomer or an olefin unsaturated monomer in an inert diluent and the catalyst system is typically supported. The gas phase process is similarly carried out by any method known to be suitable for ethylene homopolymers or copolymers prepared using supported catalysts and prepared by coordination polymerization. Exemplary embodiments include U.S. Patents 4,543,399, 4,588,790, 5,028,670, 5,352,749, 5,382,638, 5,405,922, 5,422,999, 5,436,304, 5,453,471, and 5,463,999, and international patents. It may be found in WO 94/28032, WO 95/07942 and WO 96/00245. Each is incorporated by reference in US patent practice. Typically the process is carried out at a pressure of about 7000 kPa or less, typically about 690 to 2415 kPa, at about −100 to 150 ° C., preferably at about 40 to 120 ° C. Preference is given to a continuous process using a recycle stream as the fluidized bed and fluidized medium.

Slurry polymerization processes in which the immobilized catalyst system of the present invention can be used typically require that the polymerization medium is a liquid monomer such as propylene, or a hydrocarbon solvent or diluent, advantageously aliphatic paraffins such as propane, isobutane, hexane, Heptane, cyclohexane, or the like or aromatic, for example toluene, are disclosed. The polymerization temperature is low, for example less than 50 ° C., preferably considered 0 to 30 ° C. or higher range for example about 120 ° C. or less, preferably 50 to about 80 ° C. or any range between both values disclosed. Can be. The pressure can vary from about 100 to about 700 psia (0.76 to 4.8 MPa). Further description is disclosed in US Pat. Nos. 5,274,056 and 4,182,810 and WO 94/21962, which are incorporated herein by reference in accordance with US patent practice.

Generally, the polymerization temperature for solution, bulk or supercritical polymerization processes can vary from about -50 to about 250 ° C. Preferably reaction temperature conditions are -20-220 degreeC, More preferably, it is less than 200 degreeC. The pressure is about 1 mmHg (0.1333 kPa) to 2500 bar (2.5 × 10 ⁵ kPa), preferably 0.1 to 1600 bar, most preferably 1.0 to 500 bar. If a low molecular weight copolymer is pursued, for example up to 10,000 M _n , it will be suitable for the reaction to be carried out at temperatures above about 0 ° C. and pressures below 500 bar.

As will be apparent to those skilled in the art, the catalyst compounds and components of the present invention may be used using series or parallel reactors utilizing one or more such catalyst systems or components to form one or more copolymers of the present invention, or Polymer blends are prepared that include blends with other polymers having properties associated with blends that broaden the polydispersity to improve processing of the polymer composition and improve the impact strength of the polymer blend composition.

In the process methods disclosed above for the catalysts of the invention disclosed herein, the unsaturated monomers, ie olefins or ethylenically unsaturated monomers, are polymerized to form a polymer product having a molecular weight (weight average or M _w ) of about 500 to about 3 × 10 ⁶ . . More typically, the polymer product will have an M _w of about 1000 to about 1.0 × 10 ⁶ . Suitable unsaturated monomers include ethylene, C ₃ -C ₂₀ α-olefins, C ₄ -C ₂₀ gem-substituted olefins, C ₈ -C ₂₀ aromatic substituted α-olefins, C ₄ -C ₂₀ cyclic olefins, C ₄ -C ₂₀ non-conjugated diolefins or C ₂₀ -C ₁₀₀₀ , and the vinyl and vinylidene terminated macromers. Preferably the polymer product may be any polyethylene homopolymer, ethylene copolymer, in particular polyethylene plastomer and elastomer. And, considering the known resistance of the catalyst to polar monomers, the ethylenically unsaturated polar monomers will be further polymerized or copolymerized. Preferred polar monomers include C ₄ -C ₂₀ olefins comprising functional groups such as esters, carboxylates, nitriles, amines, amides, alcohols, halide carboxylic acids and the like. More preferred are vinyl esters, halides and nitriles. Also suitable are the masked monomers of US Pat. No. 4,987,200.

Another important property of the polymers of the invention is their composition distribution (CD). The measurement of the composition distribution is the "composition distribution width index (CDBI)". CDBI is defined as the weight percent of copolymer molecules having a comonomer content within 50% of the median total molar comonomer content (ie 25% on each side). The CDBI of the copolymer is readily determined using known techniques for isolating individual fractions of copolymer samples. One such technique is described in Wild et al., J., et al. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and US Pat. No. 5,008,204.

To determine the CDBI, a solubility distribution curve is first generated for the copolymer. This can be done using the data obtained from the TREF technique disclosed above. This solubility distribution curve is a plot of the weight fraction of the dissolved copolymer as a function of temperature. This is converted into a weight fraction versus composition distribution curve. To simplify the relationship between the composition and the elution temperature, the weight fraction is estimated to have M _n of 15000 or greater, where M _n is the number average molecular weight fraction. Low molecular weight fractions generally represent minor portions of the polymers of the invention. The remainder of this specification and the appended claims maintain this practice assuming that all weight fractions in the CDBI measurement have an M _n of at least 15000.

From the weight fraction versus composition distribution curve, the CDBI is determined by establishing what weight percent of the sample has a comonomer content of less than 25% of each median comonomer content. Further details of determining the CDBI of the copolymer are known to those skilled in the art. See, eg, PCT Patent Application WO 93/03093, published February 18, 1993.

In one embodiment the polymer of the invention is generally from 50 to 99%, preferably from 50 to 85%, more preferably from 55 to 80%, even more preferably from more than 60%, even more preferably from more than 65% It has a range of CDBIs. Obviously, changing the operating conditions of the process used and using other catalyst systems results in higher or lower CDBI.

All molecular weights are weight average molecular weights unless stated otherwise. Molecular weights (weight average molecular weight (M _w ) and number average molecular weight (M _n )) are measured by gel permeation chromatography and unless otherwise stated, Waters 150 gel permeation chromatography equipped with differential refractive index detector (DRI) Graphics are used and calibrated using polystyrene standards. Samples are run in 1,2,4-trichlorobenzene (145 ° C.) using three Shodex GPC AT-80 M / S columns in series. This general technique is described in "Liquid Chromatography of Polymers and Related Materials III", J. Cazes Ed., Marcel Decker, 1981, p. 207. No corrections were made for column dispersion, but data for generally accepted standards, such as National Bureau of Standards Polyethylene 1475, were calculated in M _w / M _n when calculated from elution time. Accuracy of 0.1 units. This numerical analysis was performed using Waters Corporation's Expert ease software. M _w by GPC-VIS was measured using Waters 150 gel permeation chromatography equipped with a Viscotek 150R detector and calibrated using polystyrene standards. Samples were performed in 1,2,4-trichlorobenzene (135 ° C.) using four Shodex AT802, 803, 804 and 805 columns in series. This general technique is disclosed in RU Lew, P. Cheung, ST Balke and TH Moruy, Journal of Applied Polymer Science, 1993, 47, 1685 and 1701, incorporated herein by reference. Calibration for column dispersion was performed using pentacontan as a standard.

The branching index g 'is defined in Equation 1 below:

Where

[η] _b is the inherent viscosity of the branched polymer,

[η] _l is the intrinsic viscosity of a linear polymer having the same molecular weight as branched.

This definition is clear for monodisperse polymers. When applied to polydisperse whole polymers, branches and linear materials having the same viscosity-average molecular weight must be compared to account for different polydispersities. This latter complexity can be avoided in the GPC-VIS method, since the intrinsic viscosity and molecular weight are measured at individual elution volumes, which almost certainly includes narrow dispersed polymers.

The factor g 'may be associated with another branching index, g, using equation (2):

g '= g ^k

Where

g is the ratio of the mean square radius of the helix of the branched and linear polymer of the same molecular weight.

The index k is expected to vary from 0.5 to 1.5 depending on the type of branching structure present in the material. The value k = 0.7 has recently been used in the literature for LDPE. This value was also used in the study of the copolymer model. Different k values have been used in the literature by different authors.

The Zimmm-Stockmayer theory provides a means of the following equation (3) to correlate the g factor with the amount of long chain branching, N _w :

Finally long chain branching frequency is determined using Equation 4:

Where

M is the molecular weight.

The calculation is based on three main control assumptions.

The presence of short chain branches (eg butyl, hexyl branch) is ignored, which causes to overestimate the amount and frequency of long chain branches. The influence of this assumption on the accuracy of the calculation will depend on the amount of short-chain branches present in the material.

The index k is known exactly for the material under consideration and does not change with respect to the molecular weight distribution. Clearly, the choice of k will greatly affect the accuracy of the final guess of the amount and frequency of long chain branches.

The Jim-Stockmeyer relationship is applicable for the same polymer in the solvent used for GPC-VIS but not for theta solvent, although it is derived for the so-called theta in the solvent.

Since these assumptions have not been tested for the polymers contemplated herein, the reported values for the amount and frequency of long chain branches (hereafter referred to as branches) should be considered as estimates, not direct and accurate measurements of the true value. Nevertheless, the values can be advantageously used to compare different materials with one another.

The main advantage of the mixed catalyst of the present invention is that the blend can be produced in a single reactor without the difficulties and costs associated with additional physical blending steps after the preparation of the polymer in the reactor or reactors. Polymers with very different viscosities than high polymers are well known in the literature as difficult to mechanically blend. If the polymer chains are mixed at the molecular weight level during the polymerization process using a mixed catalyst, these problems can be avoided.

Since the late transition metal catalyst reacts differently with the metallocene or typical Ziegler-Natta catalyst for reactor conditions, the mixed catalyst of the present invention offers new opportunities to control the molecular weight distribution and the composition distribution of the polymer blend. The ability to select the appropriate reactor conditions requires the identification and understanding of the behavior of the late transition metal catalyst in the presence of other transition metal catalysts. In this respect, the present applicant has discovered that there is a surprising synergistic effect between the catalyst components of the catalyst mixtures of the present invention, resulting in unexpected reactions to catalyst reactor conditions and leading to novel and useful polymer products.

Applicants have found a clear difference between late transition metal catalysts and metallocene or Ziegler-Natta catalysts depending on how they react to changes in reactor conditions. For example, late transition metal catalysts exhibit enormous changes in the branching content of their polymers as reactor temperatures change (see Examples P1-3 to P1-5, for example). In contrast, metallocene or Ziegler-Natta catalysts exhibit much less change in branch content as the reactor temperature changes (because branch content depends on comonomer incorporation). Similarly, the branching content in polymers made with late transition metal catalysts is much more dependent on ethylene pressure or concentration than transition metal metallocene or Ziegler-Natta catalysts (see Examples P4-1 to P5-5). have). It also indicates that the presence of comonomers has a much lesser effect on the branching content in later transition metal catalysts than transition metal metallocene or Ziegler-Natta catalysts (co-pending U.S. patent application, filed June 17, 1997). Reference may be made to Examples P3-1 vs. P3-3 and P3-2 vs. P3-4 in Subtitle (Agency Document No. 96B035).

The present applicant found that the late transition metal catalyst was unexpectedly insensitive to chain transfer agents such as H ₂ , silane, isopropanol and the like (Examples P1-1, P1-2, P1-3, PC-8, P6-1 to P6-3, P6-4, P8-2 and P7-3). On the other hand, typical Ziegler-Natta and metallocene catalysts are known to be very sensitive to these chain transfer agents. In fact, H ₂ is often used in commercial reactors to control the molecular weight of the polymer product. For catalyst systems using alcohols such as isopropanol as chain transfer agent, alumoxane or other organoaluminum activator must be included as a component. Because of the different reaction of the catalyst to H ₂ and other chain transfer agents, new methods of controlling the molecular weight distribution are possible for the mixed catalyst of the present invention. Reactor conditions are selected to obtain the desired molecular weight from the later metal components of the mixture, and chain transfer agents are used to control the molecular weight of the metallocene and conventional Ziegler-Natta catalysts.

Often the molecular weight and composition distribution of the polymer blend is surprising. The comonomer composition distribution curve was determined by the TREF method for the batch polymerization example shown in Table 6a, where the characteristic data is shown. Clearly clear peaks corresponding to late transition metal catalysts or metallocenes were observed in all cases as illustrated in FIGS. 1 and 2, which show traces of Examples P2-2 and P2-3, respectively. Comparative Examples PC-1 and PC-2 show that the metallocene catalyst produces 2% highly branched (non-crystallized) polymers. Clearly, the left peak (low temperature eluting) corresponds to the late transition metal catalyst (PC-3) and the high temperature eluting polymer corresponds to the metallocene catalyst. Examples P2-1 and P2-2 exhibit unexpected behavior of mixed catalyst systems. Data from the individual component catalysts PC-3 indicate that 22% of the polymers isolated by contacting ethylene and mixed catalyst S-6 (Example P2-1, no hexene) were TM-4 (29 mole% of active transition metal compound). From the 3.14 mmol Ni x 0.65 g PE / mmol Ni = 2.0 g or 22% of the observed 9.2 g yield. However, TREF represents only 6%. In addition, catalyst S-7 utilizes a different ratio of TM-4 to TM-5 (94% TM-4) and yields much smaller ratios of calculated versus observed results (46% vs. 29%) of Ni derived polymers. Indicates. Examples P2-4 and P2-6 exhibit similar unpredictability when using different ratios of TM-4 to TM-6 (S-8, S-9). The large difference in the observed proportions of the polymer components is also due to ethylene / hexene copolymerization to ethylene homopolymerization (P2-2 to P2-3, P2-4 to P2-5, P2-6 to P2-7) for different catalyst pairs. It is observed when comparing. The data indicate that the polymer composition from the mixed catalyst cannot simply be expected from the behavior of the individual components.

In Example M1, the metallocene is mixed with a low M _w / oligomer produced Ni catalyst and the resulting polymer product has only one peak in GPC, ie, a peak with M _w of 121000. M _w was 57,000 when the same metallocene was run alone in Control Example C1. The presence of the Ni catalyst surprisingly increases the M _w ability of the metallocene as well as the presence of ethyl branches in the polymer product suggest that the oligomers produced by the Ni catalyst are incorporated by the metallocene. Other low M _w late transition metal catalysts may be selected to increase this synergistic effect (eg one or more R on E is phenyl or meta- and / or para-substituted phenyl).

Examples M2 and M3 show that this effect also occurs for vinyl or vinylidene terminated macromers produced by late transition metal catalysts. In Comparative Example C1, the polymer produced by pure metallocene TM-8 was characterized by a g 'value of 0.96 and 0.24 long chain branches per molecule compared to pure linear polyethylene. In Examples M2 and M3, the same metallocene was run using Ni catalyst TM-7 at two different catalyst ratios. Mixed catalyst systems produce blends with increased long chain branches (0.65 and 0.72 long chain branches per molecule) and reduced g'values (0.89 and 0.88 compared to pure linear polyethylene) compared to polymers produced with metallocene TM-8 alone. It was. Increased long chain branching of these polymers and blends will provide improved processability and rheological properties.

Example M9 can be produced from mixing two different late transition metal catalysts (low M _w / oligomer-producing catalyst TM-7 and high M _w catalyst TM-11) with improved M _w properties induced by a mixed catalyst. And that the effect also works in the case of propylene polymerization. The catalyst mixture produced a monomodal polymer product of M _w = 504,000 compared to the polymer produced with M _w = 162,000 (measured in Comparative Example C9) alone with TM-11. In Example M7, the late transition metal catalyst TM-2 is mixed with a typical Ziegler-Natta catalyst S-12. The properties of the polymers prepared from the catalyst system alone were measured in Examples C7 and C8. The mixture gives two M _w peaks in GPC data corresponding to 10,700 (compare 13,000 in Example C7) and 191,000 (compare 86,000 in Example C8). Surprisingly, the M _w of one catalyst polymer was lowered in the mixture, while the M _w of the other catalyst polymer was elevated.

Polymer blends prepared using the mixed catalyst of the present invention may have advantageous properties for single polymer components. For example, US Pat. Nos. 5,382,630 and 5,382,631 have molecular weights where the blend of low molecular weight, low comonomer content ethylene / α-olefin copolymers and high molecular weight, high comonomer content ethylene / α-olefin copolymers is equal to the average of the blends. And more properties than single component ethylene / α-olefin copolymers having a comonomer content. Mixed late transition metals and metallocene or Ziegler-Natta catalysts can be used to obtain this distribution of polymer chains in a single reactor. Metallocene or Ziegler-Natta catalysts produce low molecular weight chains containing less branches, whereas late transition metal catalysts select catalysts and conditions to produce high molecular weight branched polymers that behave as if they have a high comonomer concentration.

In a variation of this strategy, the transition metal catalyst component and reactor conditions can be selected to provide blends of polymer products having similar molecular weight but with different compositions. Preferably, the metallocene or Ziegler-Natta catalysts can make chains containing less comonomers, while the late transition metal catalysts can make branched chains. In this case, the molecular weight distribution may be narrow but the composition distribution may be wide. Polymer products of this form are produced by catalyst mixtures S-8 and S-9 in Examples P2-4 to P2-7. In all four examples, the molecular weight distribution of the resulting polymer is very narrow (2.31 to 4.19), while the composition distribution is distinctly wide.

In another aspect of the present invention, U.S. Pat.Nos. 5,281,679 and 5,359,015 provide improved melt processability and flow characteristics for a broad molecular weight distribution polymer blend produced in a reactor using a mixture of catalysts that produce a range of polymer molecular weights. Indicates what is observed. Examples M2 to M5 produce blends of this type. TM-7 is a late transition metal catalyst that produces a relatively low molecular weight. In these examples, TM-7 is each independently mixed with metallocene or other late transition metal catalysts having a range of molecular weight capabilities. The resulting molecular weight distribution is very wide: 35.3, 12.2, 103 and 25.3.

Similarly, propylene and α-olefins can be polymerized into highly preferred polymer blends by mixed catalyst systems. For example, a mixed catalyst system is characterized in that a single reactor polymerization of α-olefins is obtained from high molecular weight, stereoregular polyolefins (eg isotactic polypropylene) (metallocene or Ziegler-Natta catalyst components similar to ethylene / α-olefin polymers). ) And atactic polymer (from the late transition metal catalyst component). Depending on the relative amounts of product from each catalyst, the product may be thermoplastic olefin (TPO: 6 to 13 mole percent polymer from later metal catalysts), impact copolymer (ICP: 13 to 30 mole percent polymer from later metal catalysts). ) Or a thermoplastic elastomer (TPE: 30 to 60 mole percent polymer from a late transition metal catalyst). In Examples M7 and M8, isotactic polypropylene is produced by Toho Ziegler-Natta catalyst (S-12) and metallocene (TM-8) catalyst, respectively, while late transition metal catalyst (TM-) 2) produces polymers similar to ethylene / propylene copolymers having ethylene concentrations of 36 and 65 mole% equivalents, respectively.

The wide molecular weight distribution polymer product is produced from a mixed catalyst system comprising a late transition metal catalyst system and a transition metal metallocene catalyst system or one of a different late transition metal catalyst system. The wide molecular weight distribution polymer prepared from the mixed transition metal catalyst system of the present invention is preferably about 0.5 to 2.2 times larger, more preferably about 0.5 to 2 times larger, most preferably than the weight average molecular weight of the polymer fractions produced from other catalyst systems. Preferably having an average molecular weight of the polymer fraction resulting from the late transition metal catalyst system about 0.5-1.75 times larger.

Bimodal polymer products are produced from mixed catalyst systems comprising a late transition metal catalyst system and one of a transition metal metallocene catalyst system or another late transition metal catalyst system. The bimodal polymers produced from the mixed transition metal catalyst systems of the present invention are preferably about 1.5 to 25 times larger than the weight average molecular weight of the polymer fractions produced from other catalyst systems, more preferably about 1.5 to 15 times larger, most preferred. Preferably a weight average molecular weight of the polymer fractions produced from about 1.5 to 10 times larger late transition metal catalyst systems.

The multimodal molecular weight distribution polymer uses a mixed catalyst system comprising a late transition metal catalyst system and a Ziegler-Natta catalyst system; Or using a mixed catalyst system comprising a mixture of a late transition metal catalyst system and one or more other catalyst systems; Or using a mixed catalyst system comprising a late transition metal catalyst system and a transition metal metallocene catalyst system or other late transition metal catalyst system, changing the profile of the reactor (eg, temperature, ethylene concentration, chain transfer concentration, etc.) Or using a series of reactors; Or a combination thereof.

The molar ratio of polymer fractions resulting from mixed transition metal catalyst systems can also vary. The molar ratio of the polymer fraction produced from the late transition metal catalyst to the catalyst produced from the other catalyst system is preferably about 99: 1 to 1:99, more preferably about 90:10 to 1:99, and even more preferably about 25: 75 to 1:99, most preferably about 10:90 to 1:99. When the monomer feed is propylene and the second catalyst component can produce crystalline polypropylene, the most preferred molar ratio of the polymer fraction produced from the late transition metal catalyst system to the polymer produced for the other catalyst system is that of the thermoplastic olefin formation. About 3:97 to 18:82, more preferably 6:94 to 13:87; For impact copolymer formation preferably about 10:90 to 35:65, more preferably 13:87 to 30:70; And from about 25:75 to 65:35, more preferably from 30:70 to 60:40 for thermoplastic elastomer formation.

In one aspect of the invention, when the polymer product molecular weight distribution is wide and in bimodal, the composition distribution width index of the polymer may be narrow, and the preferred composition distribution width index is about 70% to 100%, more preferably about 80% to 100 % And most preferably 85% and 100%, with values above 80% being most preferred.

In another embodiment of the present invention, when the polymer product molecular weight distribution is wide or bimodal, the composition distribution width index of the polymer may be wide at right angles, which means that the high molecular weight polymer fraction will have a higher branching content and the low molecular weight polymer fraction It has a lower branching content. These polymers preferably have a composition distribution width index of about 25 to 85%, more preferably about 40 to 85% and most preferably about 50 to 85%.

In still another aspect of the present invention, the polymer molecular weight distribution produced from the mixed catalyst system is narrow and the composition distribution width index is wide. Preferred molecular weight distribution is about 1.5 to 4.5, more preferably about 2.0 to 3.5, most preferably about 2.0 to 3.0. The polymer composition distribution width index is preferably about 25 to 85%, more preferably about 40 to 85% and most preferably about 50 to 85%.

Preferred olefin compositions when the late transition metal catalyst system is selected to produce α-olefins and the other catalyst component is a transition metal metallocene catalyst system or a Ziegler-Natta catalyst system are from about C ₄ to C ₃₀ , more preferably about C ₄ to C ₂₀ and most preferably C ₄ to C ₁₀ . Depending on the ratio of the two catalyst systems used, the amount of comonomer incorporation is about 90 to 1 mol%, more preferably about 50 to 1 mol% and most preferably about 30 to 1 mol%.

The olefins of the preferred macromers when the late transition metal catalyst system is selected to produce vinyl and vinylidene terminated macromers and the other catalyst component is a transition metal metallocene catalyst system, a Ziegler-Natta catalyst system or a late transition metal catalyst system. The composition is about C ₃₀ to C ₁₀₀₀ , more preferably about C ₅₀ to C ₈₀₀ and most preferably C ₁₀₀ to C ₅₀₀ . Depending on the ratio of the two catalyst systems used, the macromer incorporation is about 100 branches / 1000C to 0.005 branches / 1000C, more preferably about 10 branches / 1000C to 0.01 branch / 1000C, most preferably about 3 branches / 1000C to 0.01 Branch / 1000C. In addition, it is most preferred that the resulting polymer has a g 'of no greater than 0.95 relative to the linear polyolefin.

The following examples for polymerization methods 1-8 were carried out with catalyst systems derived from the complexes of Table 1 shown below.

This example illustrates heterogeneous and homopolymerization using the catalyst system according to the invention. Processes for preparing supported catalysts for heterogeneous processes are described. Examples of gas phase polymerization, slurry polymerization and solution polymerization are shown.

General support method

Aluminoxanes such as methylalumoxane or modified alumoxanes or other suitable activators such as Al (CH ₃ ) ₃ , Al (CH ₂ CH ₃ ) ₂ Cl, B (C ₆ F ₅ ) ₃ , [C ₆ H ₅ NMe ₂ H] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- , [(C ₆ H ₅ ) ₃ C] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- , [H] ⁺ [BF ₄ ] ^- , [H] ⁺ [PF ₆ ] ^- , [Ag] ⁺ [BF ₄ ] ^- , [Ag] ⁺ [PF ₆ ] ^- , or [Ag] ⁺ [B (C ₆ F ₅ ) ₄ ^- is mixed with one or more transition metal complexes in a suitable solvent to form a precursor solution. A suitable support, preferably a porous support, is charged to the vessel and the precursor solution is added with stirring. The mixture is shaken by hand using a spatula, with a rotating stirrer with wire loops, such as a Kitchen Aid dough mixer, with a metal blade rotating at high speeds, such as a Wehring mixer, with a spiral ribbon blade mixer. , By mixing, by fluidized bed mixing, by mixing with a paddle or propeller blade or other suitable means on the stirring shaft. The total amount of solvent used to form the precursor suspension or solution is less than the pore volume of the support to be infiltrated with initial wetness, or is above the pore volume of the support to form a slurry, or the flow of the solution-finely divided support mixture This may be an amount between them that is neither free nor slurryed. The solution may be added to the support as appropriate depending on the mixing method, or vice versa, to the support. If desired, the liquid may be removed by purging under inert gas or vacuum.

Support method

Aluminoxane or a suitable activator was mixed with the transition metal complex in toluene to form a precursor solution. The solution was filled into the vessel, the porous support was added all at once, and the mixture was stirred by hand using a spatula. The total volume of the precursor solution was larger than the pore volume of the support, but was not sufficient to reach the gel point or to form a slurry (about 100-200% pore volume). The solvent was removed at vacuo (pressure <200 mTorr) and ambient temperature for about 12-16 hours overnight.

The aluminoxane used was 30% by weight of methyl aluminoxane, supplied in toluene, from Albemarle. Silica was MS948 (1.6 cc / g PV (PV = pore volume), Davison Chemical Company) already heated to 600 ° C. for 3 hours at N ₂ , and toluene was free of air and moisture from exon chemical.

Method 1: Continuous Fluidized Bed Gas Phase Polymerization

Ethylene polymerization studies summarized in Tables 3 and 4 of continuous circulating fluidized-bed gas phase polymerization reactors under the conditions described in co-pending US patent application Ser. No. 08 / 466,547 and WO 96/00245, filed June 6, 1995. Used for. Approximate dimensions of the reactor cross section above the distributor plate and below the glass head were 4 inches (10.2 cm) in diameter and 24 inches (61.0 cm) in length. The total operating pressure is 314.7 psia (2170 kPa) (gas composition described in Table 2, the rest is N ₂ ) and polymer samples were collected after several bed conductions. Detailed method descriptions are set forth in Table 3 and the product characteristic data is shown in Table 4.

Method 2: Semibatch Slurry Polymerization

The conditions of the polymerization example are shown in Table 5. The polymerization was carried out in 400 ml of anhydrous hexane in a nitrogen filled 1 liter Zipperclave reactor (Autoclave Engineer) with an external temperature control jacket. Among the glove boxes, usually 50-200 mg of filler of supported catalyst was filled in the short length of the SS tube between two ball valves, followed by a small bomb containing 20 ml of anhydrous hexane. This apparatus was attached to the reactor under N ₂ filling. Unless otherwise specified, a cocatalyst (0.200 ml of 25 wt% triethylaluminum in heptane) was injected into the reactor with comonomers and, where noted, the mixture was heated to operating temperature with stirring. Stirring was stopped and the catalyst was flushed into the reactor with hexanes reinforced with ethylene or nitrogen pressure. When the reactor reached the adjusted operating pressure corrected for solvent vapor pressure, the agitation was immediately resumed.

After sufficient reaction took place, the reactor was evacuated and the contents poured into a beaker with 1 liter of stirred acetone under air and filtered. Alternatively, the solvent can be removed under vacuum or by colliding with a nitrogen stream. The separated polymer sample was then dried overnight in a vacuum drying oven at about 50 ° C.

1 and 2 contain CD traces of the single component polymers produced in Examples P2-2 and P2-3 of Table 5. Polymerization P2-1 to P2-7 used a mixed catalyst. The CD trace of the polymer clearly shows that two distinct polymer components are produced, as shown in Figures 1 and 2, where the high temperature elution fraction corresponds to the metallocene and the low temperature peak corresponds to the late transition metal catalyst. Increasing the amount of comonomer reduced the elution temperature of the metallocene induced peak consistent with the increased branching content. Further areas of increased high temperature peaks showed increased activity of metallocenes compared to late transition metal complexes. The decrease in the relative load of the metallocene resulted in a more uniform distribution under the same conditions.

Method 3: semi batch solution / suspension polymerization in hexane

The polymerization was carried out as in Method 2 except for the following. Triethylaluminum was not used. Instead, 10% by weight of methyl aluminoxane in Witco's toluene was introduced into the reactor as both scavenger and activator. The transition metal compound was introduced into the reactor as a solution in toluene but other solvents such as difluorobenzene and methylene chloride can be used.

Method 4: semi batch solution / suspension polymerization in toluene

This is the method of Method 3, except that toluene is used as the polymerization solvent. A catalyst solution was prepared using 1,2-difluoro benzene as the solvent when the late transition metal complex used was TM-2.

Method 5: semi-batch solution / suspension polymerization of Brookhart

This is the method of Comparative Example of Brookhart et al. Disclosed above. Brookhart's polymerization data, as shown in Tables 7 and 8, indicate that the polymer molecular weight and yield are independent of ethylene pressure. However, Examples P4-1 to P4-5 show distinct differences in yield and molecular weight when there is a difference in pressure.

Method 6: Semi-Batch MAO Activation Solution / Suspension Polymerization in Toluene Using Polymerization Modifiers

The conditions of the polymerization example are shown in Table 9. This is the same method as Method 3 above, except that a polymerization modifier such as the indicated number of micromoles of isopropanol was introduced into the reactor prior to catalyst addition.

The examples shown in Tables 3, 4, 9 and 10 show that the M _w of the polymer produced by the catalyst of the present invention is not affected by the presence of silane or hydrogen. They are well known to reduce molecular weight in typical coordination polymerization catalysts (see, eg, Marks, JACS 1995, 117, 10747 and references herein). Thus, it is possible to control the molecular weight of the latter polymer component independently of the late transition metal polymer component.

Method 7: Semi-batch Uncoordinated Anion (NCA) Activation Solution / Suspend Polymerization in Toluene with Polymerization Modifiers

The conditions of the polymerization example are shown in Table 11. This is a non-coordinating anion, in this case than methyl alumoxane ^{_{[PhNMe 2 H +] [B}} (C 6 F 5) 4 -] and is the method 6 except that the use late transition activate the metal complex prior to addition to the reactor the Is the same as the method. These reactions were performed in 500 ml autoclave in 200 ml toluene.

Having a formulation capable of terminating the polymerization reaction is particularly useful for the operation of commercial processes. The study of the inventors showed that catechol borane effectively suppresses the polymerization activity. Trimethoxysilane substantially prevented the polymerization activity. See Table 9.

Method 8: Semi-batch uncoordinated anion (NCA) activating solution / suspension polymerization in toluene with polymerization modifiers and scavengers

The conditions of the polymerization example are shown in Table 11. This is identical to the method of method 7 above, except that a further 10 μl solution of 25 wt% triisobutylaluminum in heptane was added to the reactor.

The presence of both trimethoxy silane and isopropanol reduced the molecular weight of the resulting polymer and further isopropanol did not reduce the polymerization activity. In addition, the addition of triisobutylaluminum substantially increased the polymer yield. See Tables 11 and 12.

Mixed Catalyst Example

Paddle stirrer, external water jacket for temperature control, controlled supply of anhydrous nitrogen, ethylene in addition to direct supply of propylene, 1-butene and hexane, and of other solvents or comonomers, transition metal compounds and activators / promoters The polymerization was carried out in a 1 liter autoclave reactor with a diaphragm inlet for introduction. The reactor was dried prior to use and thoroughly degassed. The activator used was 10% by weight of methylalumoxane of albemal (A-1), 15% by weight of aluminum sesquichloride or Akzo in hexane of Texas alkyl (A-2). 25 weight percent triethylaluminum (TEAL) in heptane of (A-3) was included. The transition metal compounds used are vanadium oxide trichloride (TM-10), Toho 133, a typical Ziegler-Natta polypropylene catalyst used with cyclohexylmethyldimethoxy-silane as external donor (S-12), dimethylsilyl -Bis (tetrahydroindenyl) zirconium dichloride (TM-8), dimethylsilyl (tetramethylcyclopentadienyl) cyclododecylamido-titanium dichloride (TM-9) and the following Group 10 catalysts were included: :

Typical mixed catalysts consisted of adding 400 ml of solvent or bulk monomer followed by the addition of an activator and the reactor equilibrated to the desired temperature. Subsequently, a transition metal compound was added. Unsupported metallocene compound was added as a toluene solution. Group 10 compounds were typically added as methylene chloride solutions. The supported catalyst was put into the reactor through a catalyst addition tube using high pressure nitrogen and / or about 10 ml of hexane. When ethylene was used, it was fed continuously at the indicated differential pressure. The polymerization was limited to the time indicated. The system was cooled rapidly and vented to stop the reaction. In some cases isopropyl alcohol was also added to the polymer sample. The solvent of the polymer was evaporated by a stream of nitrogen and the drying was terminated at 100 ° C. in a vacuum oven if necessary. Data for polymerization and polymer analysis are shown in Tables 13, 14, 15 and 16 with the following supplemental information. Examples M1 to M6 and C1 to C5 are polymerization reactions using ethylene as the only added monomer feed. Examples M7 to M9 and C6 to C9 are polymerization reactions using propylene as the only added monomer feed.

Mixed Catalyst-Example M1

This example produced a low molecular weight polymer / oligomer using a Group 10 catalyst (TM-7) and a high molecular weight polymer using a metallocene catalyst (TM-8). Standard polymerization conditions included the use of 400 ml of toluene as solvent, 10% by weight of alumoxane as activator and continued feeding of 65 psia of ethylene into the reactor. Since a small amount of TM-7 was used, the molecular weight distribution of the resulting polymer is relatively narrow, but there is a low molecular weight tail. Only small amounts of ethyl branch were detected by ¹³ C NMR (0.2 mol%).

Mixed Catalyst-Example M2

This example produced a low molecular weight polymer / oligomer using a Group 10 catalyst (TM-7) and a high molecular weight polymer using a metallocene catalyst (TM-8). Standard polymerization conditions included the use of 400 ml of toluene as solvent, 10% by weight of alumoxane as activator and continued feeding of 65 psia of ethylene into the reactor. The product produced in this example has a bimodal molecular weight distribution. GPC viscometers represent long chain branches in high molecular weight fractions at the level of 0.2 branch / 1000 C or 0.65 branch / molecule. The average g 'for the linear polyethylene was calculated to be 0.89. ¹³ C NMR data showed short-chain branches of various lengths where the dominant branch was methyl. Total short chain branching was measured at 43.7 SCB / 1000C.

Mixed Catalyst-Example M3

This example produced a low molecular weight polymer / oligomer using a Group 10 catalyst (TM-7) and a high molecular weight polymer using a metallocene catalyst (TM-8). Standard polymerization conditions included the use of 400 ml of toluene as solvent, 10% by weight of alumoxane as activator and continued feeding of 65 psia of ethylene into the reactor. The product produced in this example has a bimodal molecular weight distribution. GPC viscometers represent long chain branches in high molecular weight fractions at the level of 0.25 branch / 1000 C or 0.72 branch / molecule. The average g 'for the linear polyethylene was calculated to be 0.88. ¹³ C NMR data showed short-chain branches of various lengths where the dominant branch was methyl. Total short chain branching was measured at 39.5SCB / 1000C.

Mixed Catalyst-Example M4

This example produced a low molecular weight polymer / oligomer using Group 10 catalyst (TM-7) and a high molecular weight polymer using metallocene catalyst (TM-9). Standard polymerization conditions included the use of 400 ml of hexane as the solvent, 10% by weight of alumoxane as the activator and the continuous feeding of 65 psia of ethylene to the reactor. The product produced in this example has a bimodal molecular weight distribution. ¹³ C NMR data showed short chain branches of various lengths. Total short chain branching was measured at 18.2SCB / 1000C.

Mixed Catalyst-Example M5

This example produced a low molecular weight polymer / oligomer using Group 10 catalyst (TM-7) and produced a high molecular weight polymer using Group 10 catalyst (TM-2). Standard polymerization conditions included the use of 400 ml of hexane as the solvent, 10% by weight of alumoxane as the activator and the continuous feeding of 65 psia of ethylene to the reactor. The product produced in this example has a bimodal molecular weight distribution. ¹³ C NMR data showed short-chain branches of various lengths where the dominant branch was methyl. Total short chain branching was measured at 102SCB / 1000C.

Mixed Catalyst-Example M6

This example produced a high molecular weight polymer / oligomer using a Group 10 catalyst (TM-2) and a high molecular weight polymer using a Group 5 catalyst (TM-10). Standard polymerization conditions included continuous feeding of 400 ml of hexane as solvent, 15% by weight of aluminum sesquichloride in hexane as activator and 65 psia of ethylene into the reactor. The molecular weight distribution of the resulting polymer was narrow, with no short chain branching as measured by ¹³ C NMR. This mode and lack of branching can be attributed to the small amount of TM-2 used compared to TM-10.

Example C1

This example is a comparative example using a metallocene catalyst (TM-8) alone. Metallocene was already used in Examples M1, M2 and M3, but the reaction temperature was different from M2 and M3. Standard polymerization conditions included the use of 400 ml of toluene as solvent, 10% by weight of alumoxane as activator and continued feeding of 65 psia of ethylene into the reactor. The resulting polymer had a relatively narrow molecular weight distribution. ^No short chain branching was determined by ¹³ C NMR. GPC viscometer shows long chain branches at the level of 0.05 branch / 1000C or 0.235 branch / molecule. The average g 'for linear polyethylene was calculated at 0.96.

Example C2

This example is a comparative example using only metallocene catalyst (TM-9). This metallocene has already been used in Example M4. Standard polymerization conditions included 400 ml of toluene as solvent, 10% by weight of alumoxane as activator and 65 psia of ethylene fed continuously to the reactor. The resulting polymer had a relatively narrow molecular weight distribution. Short chain branches were not shown as measured by ¹³ C NMR.

Example C3

This example is a comparative example using only Group 10 catalyst (TM-2). Group 10 compounds have already been used in Examples M5 and M6, but only in M6 the same activator as in this example is used. Standard polymerization conditions included 400 ml of hexane as solvent, 15% by weight of aluminum sesquichloride in hexane as activator and 65 psia of ethylene continued to be fed to the reactor.

Example C4

This example is a comparative example using only Group 5 catalyst (TM-10). This Group 5 compound has already been used in Example M6. Standard polymerization conditions included 400 ml of hexane as solvent, 15% by weight of aluminum sesquichloride in hexane as activator and 65 psia of ethylene continued to be fed to the reactor. The resulting polymer had a relatively narrow molecular weight distribution. ¹³ C NMR data showed short chain branches of various lengths where the dominant branch was methyl. Total short chain branching was measured at 82.7 SCB / 1000C.

Example C5

This example is a comparative example using only Group 10 catalyst (TM-7). Group 10 compounds have already been used in Examples M1 to M5. In particular the examples used a 100 ml reactor with 40 ml of toluene, 170 mg of solid MAO (prepared from 30 wt.% MAO of Albemarel dried to solids) and 65 psia of ethylene fed to the reactor as solvent. The isolated product was an oily liquid with ¹ H NMR showing a mixture of vinyl, vinylidene, vinylene and trisubstituted end groups.

Mixed Catalyst-Example M7

This example produced a high molecular weight amorphous propylene-based polymer using a Group 10 catalyst (TM-2) and a high molecular weight using a typical Ziegler-Natta propylene catalyst using cyclohexylmethyldimethoxysilane as the external donor (SX). An isotactic polypropylene polymer was produced. Standard polymerization conditions included the use of 400 ml of propylene as both monomer and solvent, 25% by weight TEAL in heptane as activator and 28 mg of cyclohexylmethyldimethoxysilane as external donor. Ethylene was not used. The resulting material did not appear completely uniform. This appeared as a mixture of crystalline polymer and amorphous polymer. The polymer was physically kneaded before submitting for analysis. The resulting polymer mixture had a bimodal molecular weight distribution. ¹³ C NMR spectroscopy showed that the polymer contained 36 mol% equivalent of ethylene (without ethylene). The predominant (CH ₂ ) _n sequence was n = 1 (83%).

Mixed Catalyst-Example M8

This example produced a high molecular weight amorphous propylene based polymer using a Group 10 catalyst (TM-2) and a high molecular weight isotactic polypropylene polymer using a metallocene catalyst (TM-8). Standard polymerization conditions included the use of 400 ml of propylene as both monomer and solvent and 10% by weight of MAO as activator. Ethylene was not used. The product produced in this example has a narrow molecular weight distribution. ¹³ C NMR spectroscopy showed that the polymer contained 65 mol% equivalent of ethylene (without ethylene). The predominant (CH ₂ ) _n sequence was n = 1 (29%), followed by n = 2 (22%). ¹³ C NMR data showed short chain branches of various lengths where the dominant branch was methyl. Total short chain branching was measured at 157.5SCB / 1000C (149.1% methyl, 2.5% ethyl, 0% propyl, 2.1% butyl, 1.5% pentyl and 2.4% long branches).

Mixed Catalyst-Example M9

This example produced a low molecular weight polymer / oligomer using a Group 10 catalyst (TM-7) and a medium molecular weight amorphous propylene-based polymer using a Group 10 catalyst (TM-11). Standard polymerization conditions included the use of 400 ml of propylene as both monomer and solvent and 10% by weight of MAO as activator. Ethylene was not used. The product produced in this example was similar to the polymer produced using only the high molecular weight amorphous propylene-based polymer of Comparative Example C9, but the polymer molecular weight was significantly increased.

Example C6

This example is a comparative example using only Group 10 catalyst (TM-2). Group 10 compounds were already used in Example M8. Standard polymerization conditions included the use of 400 ml of propylene as both monomer and solvent and 10% by weight of MAO as activator. Ethylene was not used. The product produced in this example has a narrow molecular weight distribution. ¹³ C NMR spectroscopy showed that the polymer contained 42 mole equivalents of ethylene (without ethylene). The predominant (CH ₂ ) _n sequence was n = 1 (65%).

Example C7

This example is a comparative example using only Group 10 catalyst (TM-2). Group 10 compounds were already used in Example M7. Standard polymerization conditions included the use of 400 ml of propylene as both monomer and solvent and 25% by weight of TEAL in heptane as activator. Ethylene was not used. The product produced in this example has a narrow molecular weight distribution. ¹³ C NMR spectroscopy showed that the polymer contained 59 mole equivalents of ethylene (without ethylene). The predominant (CH ₂ ) _n sequence was n = 1 (57%).

Example C8

This example is a comparative example which produces a high molecular weight isotactic polypropylene polymer using a typical Ziegler-Natta propylene catalyst using cyclohexylmethyldimethoxysilane as external donor (SX). Standard polymerization conditions included the use of 400 ml of propylene as both monomer and solvent, 25% by weight TEAL in heptane as activator and 28 mg of cyclohexylmethyldimethoxysilane as external donor. Ethylene was not used. Tacticity was measured at 85% m dyads by ¹³ C NMR. The resulting polymer has a broad molecular weight distribution but is as wide as Example M7 and not bimodal.

Example C9

This example is a comparative example using only Group 10 catalyst (TM-11). Group 10 compounds were already used in Example M9. Standard polymerization conditions included the use of 400 ml of propylene as both monomer and solvent and 10% by weight of MAO as activator. Ethylene was not used. The product produced in this example has a narrow molecular weight distribution. ¹³ C NMR showed that the polymer contained 27 mole equivalents of ethylene (without ethylene). The predominant (CH ₂ ) _n sequence was n = 1 and no more than 5 sequences were observed.

Claims (33)

One or more late transition metal catalyst systems of Formula 1; And late transition metal catalyst systems, transition metal metallocene catalyst systems that are Group 4, 5, 6, 9 or 10 transition metal compounds with mono- or bis-substituted cyclopentadienyl ligands, and olefins by Ziegler promoters Mixed transition metal olefins suitable for olefin monomer polymerization comprising at least one different catalyst system selected from the group consisting of Ziegler-Natta transition metal catalyst systems comprising a Group 4, 5 or 6 transition metal halide or oxyhalide activated for polymerization Polymerization catalyst system: Formula 1 LMX _r Formula 2 Where M is a 9, 10 or 11 metal, L is a bidentate ligand of Formula 2, Each X independently represents a hydride radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, a halocarbyl radical, a substituted halocarbyl radical, a hydrocarbyl-substituted organometalloid radical or a halocarbyl-substituted organometalloid radical Or; Or two X are linked and bonded to a metal atom to form a metallocycle ring containing 3 to 20 carbon atoms; Or donor ligands containing neutral hydrocarbyl; Halogen, alkoxide, aryloxide, amide, phosphide or other monovalent anionic ligand; Or two X are linked to form an anionic chelating ligand; Or a donor ligand containing neutral non-hydrocarbyl atoms; r is 0, 1, 2 or 3, A is a crosslinking group containing a group 13 to 15 element, E are each independently a group 15 or 16 element bonded to M, Each R is independently a C ₁ -C ₃₀ containing radical or diradical, which is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organo No metalloid, m and n are independently 1 or 2, depending on the valence of E, p is the charge on the bidentate ligand in which the oxidation state of MX _r is satisfied. The method of claim 1, Mixed transition metal olefin polymerization catalyst system wherein at least one different catalyst system comprises a Group 9, 10 or 11 metal complex stabilized by a bidentate ligand structure and activated for olefin polymerization. The method of claim 2, Mixed transition metal olefin polymerization catalyst system activated with a total transition metal to activator in a molar ratio of 1: 1000 to 1: 1. The method of claim 3, wherein Mixed transition metal olefin polymerization catalyst system wherein the activator is alumoxane. The method of claim 3, wherein Mixed transition metal olefin polymerization catalyst system wherein the activator is a Ziegler promoter. The method of claim 3, wherein A mixed transition metal olefin polymerization catalyst system wherein the activator is an ionizing, anionic precursor compound capable of providing compatible, uncoordinated anions. The method of claim 6, A mixed transition metal olefin polymerization catalyst system wherein the non-coordinating anion is tetrakis (perfluorophenyl) boron. The method of claim 6, A mixed transition metal olefin polymerization catalyst system wherein the ionization, anion precursor compound is a halide salt of a Group 13-16 metal or metalloid. The method of claim 1, Mixed transition metal olefin polymerization catalyst system wherein at least one different catalyst system comprises a transition metal metallocene catalyst system. The method of claim 9, A mixed transition metal olefin polymerization catalyst system wherein the transition metal metallocene catalyst system comprises a Group 4 metal complex stabilized by one or more auxiliary cyclopentadienyl ligands and activated for olefin polymerization. The method of claim 9, Mixed transition metal olefin polymerization catalyst system activated with a total transition metal to activator in a molar ratio of 1: 1000 to 1: 1. The method of claim 11, Mixed transition metal olefin polymerization catalyst system wherein the activator is alumoxane. The method of claim 11, A mixed transition metal olefin polymerization catalyst system wherein the activator is an ionizing, anionic precursor compound capable of providing compatible, uncoordinated anions. The method of claim 13, A mixed transition metal olefin polymerization catalyst system wherein the non-coordinating anion is tetrakis (perfluorophenyl) boron. The method of claim 1, Mixed transition metal olefin polymerization catalyst system in which at least one different catalyst system comprises a typical Ziegler-Natta transition metal catalyst system. The method of claim 15, A mixed transition metal olefin polymerization catalyst system having a molar ratio of total transition metal to promoter of 1: 1000 to 1: 1. The method of claim 1, A mixed transition metal olefin polymerization catalyst system further comprising a solid support. The method of claim 17, Mixed transition metal olefin polymerization catalyst system activated with a total transition metal to activator in a molar ratio of 1: 120 to 1: 1. One or more ethylenes, C ₃ -C ₂₀ α-olefins, C ₄ -C ₂₀ gem-substituted olefins, C ₈ -C ₂₀ aromatic substituted α-olefins, C ₄ -C ₂₀ cyclic olefins, C ₄ -C ₂₀ non-porous A process for the polymerization of olefinically unsaturated monomers comprising contacting liquid diolefins or C ₂₀ -C ₁₀₀₀ vinyl and vinylidene end macromers with the mixed transition metal catalyst system of claim 1 to produce a polymer. The method of claim 19, A polymerization process carried out in the presence of a chain transfer agent. The method of claim 20, The polymerization method wherein the chain transfer agent is hydrogen. The method of claim 19, The polymerization method wherein the chain transfer agent is silane. The method of claim 19, And the contacting further comprises using an scavenging compound. The method of claim 23, The polymerization method wherein the scavenging compound is a Group 13 organometallic compound. The method of claim 19, A polymerization method comprising contacting under gas phase polymerization conditions. The method of claim 25, The polymerization process wherein the reactor temperature is -100 to 150 ℃ and the pressure is carried out below 7000kPa. The method of claim 19, A polymerization process comprising contacting under slurry polymerization conditions. The method of claim 27, The polymerization process wherein the reactor temperature is 0 to 120 ℃ and the pressure is carried out at 0.76 to 4.8 MPa. The method of claim 19, A polymerization process comprising contacting under solution, bulk or supercritical polymerization conditions. The method of claim 29, The polymerization process wherein the reactor temperature is -20 to 220 ° C and the pressure is carried out at 133 Pa to 250,000 KPa. The method of claim 19, Polymerization process carried out in a tandem reactor. The method of claim 19, And wherein the polymer has a weight average molecular weight of 1.5 to 10 times greater than the weight average molecular weight of the product from another catalyst system. The method of claim 19, And wherein the polymer has a weight average molecular weight of 0.5-1.75 times greater than the weight average molecular weight of the product from another catalyst system.