Start up methods for multiple catalyst systems

Methods for operating multiple excavator systems

Full description

Background of the invention

This invention relates to methods for adding multiple catalysts to a gas or slurry phase reactor, specifically for reactor operation.

reactor.

More recently in technology, attempts have been made to produce two polymers with each other at the same time in the same reactor using two different catalysts. For example, Mobil described in its international patent application under Patent Cooperation Treaty No. 99/03899 the use of a metallocene catalyst and a Ziegler-Natta catalyst in the same reactor to produce high-density polyethylene. polyethylene (HDPE) with a bimodal molecular weight distribution (MWD). However, it may be difficult to operate two catalysts simultaneously and likewise a multiple catalysts system may be difficult to operate. Thus, there is a need in technology for procedures to operate multiple catalytic systems.

U.S. patent application serial number 09/451,792, entitled “Solution Feed of Multiple Catalysts} filed on December 1, 1999, describes the use of multiple drills in a gaseous and slurry phase to produce olefins.

U.S. Patent Application Serial No. 09/3120878 filed on May 17, 1999 describes U.S. Patent No. 6,271,325 filed in

2001 AD The polymerization process in a gas or slurry phase using a supported bisamide catalyst.

General description of the invention

This invention relates to methods for adding multiple rigs to a gas-phase or slurry reactor including:

(a) Adding one or more olefins, a first catalyst, and an activator to the reactor and enabling the polymerization of the olefins, (b) obtaining a polyolefin,

(d) Mixing a second catalyst and an optional activator with the first catalyst and activator and then adding the combination to the reactor and allowing the polymerization of olefins.

In an alternative embodiment, step (b) includes determining whether the polyolefin produced in step (a) is the desired polyolefin, and if it is not the desired polyolefin, one or more reaction conditions are changed and step (b) is repeated. This is amazing.

In another embodiment, this invention relates to a method for adding multiple catalysts to a gas-phase or slurry reactor including adding one or more olefins, a first catalyst and an activator, and a second catalyst and an optional activator to the reactor, wherein all the catalysts and activators are mixed together before being added to the reactor. In a preferred embodiment, the catalyst and activator(s) are added to the reactor in a liquid, preferably a solution, slurry or emulsion.

For the purposes of this invention, the term “catalyst” means a metal compound that polymerizes olefins alone or in combination with an activator. The term “catalytic system” means a combination of a catalyst and an activator. The term “activator” is used interchangeably with the term “cocatalyst”.

Detailed description of the invention

In other embodiments, hydrogen is also added to the reactor during step (a), and it is preferable to measure the hydrogen concentration present in the reactor or gas recycle stream when the polyolefin desired in step (b) is produced and thus does not change the hydrogen concentration hydrogen during step (d) so that it differs from the concentration measured when the polyolefin desired in step (b) transpires, more or less by more than 50%. It is preferable not to change the hydrogen concentration during step (c) so that it differs Regarding the concentration measured when polyolefin is produced in step (b) by more than 40 plus or minus, it is preferable that it does not exceed 30%, it is preferable that it does not exceed 20%, and it is most preferable that it does not exceed 10%.

In another preferred embodiment, when the polyolefin produced during step (c) is an undesired polyolefin, then the ratio of catalyst one to catalyst two added to the reactor can be varied.

In another embodiment we further include adding a third catalyst (or more) and optionally an activator to the reactor. This can optionally be done after determining whether the polyolefin produced in step (c) is the desired polyolefin. If it is not the desired polyolefin, then one or more reaction conditions can be changed until the desired polyolefin is produced. In an alternative embodiment, step (c) also includes an additional catalyst.

Start-up method of two-mode systems using solution feed

Contains two catalysts

Although the following examples illustrate the production of polyethylene (PE) using multiple catalysts, preferably solution catalysts , the invention can also be applied to any polyolefin produced with more than two catalysts. Typically, the resulting polyolefins have a molecular weight distribution (molecular weight distributions (MWD'S).

broad, bi-modal or multimodal. The operating procedures described below can be applied to all polymerizable monomers and mixtures of these monomers such as propylene, ethylene, styrene and polar monomers.

In a preferred embodiment, a catalytic system capable of producing polyethylene (preferably bimodal or broad MWD polyethylene) includes two or more different catalysts. The two catalysts or catalysts have different, preferably significantly different, responses to hydrogen and/or the comonomer. There are also usually one or more activators in the system to activate the catalysts. Examples of different activation and feed methods are shown below. In preferred embodiments according to the invention, a first catalyst produces a low molecular weight resin (such catalyst is referred to as a low molecular weight catalyst), and a second catalyst produces a high molecular weight resin (such catalyst is referred to as a high molecular weight catalyst). These catalysts are located together in the same reactor to produce a resin that has a broad or bimodal overall molecular weight distribution. It is preferable to mix multiple catalysts and/or activators together and then add them to the reactor.

The following reactor operating techniques are described in relation to a solution catalyst feed system, but can be applied to emulsion, slurry, liquid, and/or supported powdered and/or portable catalyst systems. The following operating techniques can be applied to any of the activation and feeding methods described below. It is preferable to use the following methods when the reactor is at a point where catalyst feeding can be initiated.

A problem with running two resin components in the same reactor is that the resin properties of one of the components must often be fixed. For example, in many cases it is desired that the Melt Index (i), which is an indirect measurement of the molecular weight, of a low molecular weight (LMW) resin be within a certain range. With the formation of two resin components

At the same time and in the same reactor, the LMW (or high molecular weight (HMW) resin flow index) is difficult to measure directly. In most cases, catalyst poisons or analyzer replacement may result in the production of a large amount of resin with incorrect LMW or HMW properties.

In addition, it should be taken into account that when a gas-phase reactor is first operated, reaction rates become slower as the built catalyst of the invention accumulates in the reactor. As expected, the residence time changes from operation to steady state operation. For a bimodal catalytic system, the residence time or space time yield (STY) affects the properties of the final product, such as the flow index (I21). This is thought to be because, in most cases, the catalyst kinetics are different. In addition, it has been observed that catalysts with different kinetic constants and/or half-lives, along with residence time effects, cause a change in the production of the polymer product. To compensate, or preferably to control, these changes, it is preferable to perform an on-line control of the feed stream from the catalysts and/or activators to the reactor at different rates and/or volumes.

In a preferred embodiment the multiple catalysts have identical or nearly identical kinetic behavior. In a preferred embodiment, the difference in kinetic profiles or half-lives is 50% or less, preferably 40%, preferably 30%, and preferably 10%.

In preferred embodiments, the following operating methods may be used.

Method 1

We fire a first start method that can be applied to a solution of catalysts by starting one catalyst feed and a co-catalyst before starting the second catalyst feed. This first method allows determining the reactor conditions necessary to produce the correct LMW or HMW resin component. In this method, the low molecular weight catalyst (LMWC) or catalyst can be started first

High molecular weight catalyst (HMWC). It is preferable to start first with LMWC, as the process produced by direct operation using C- may produce significant amounts of gels in the film blown layer of the resin (and usually, two or more resin components). When If the correct gas-phase reactor conditions are known (or may be known before operation), the second catalyst component can be operated after the reaction from the first component has occurred. If the kinetic parameters of the catalysts are known to produce a particular polymer, the catalyst feed rates can be adjusted when the reaction occurs to be according to the on-specification at the full production rate. Alternatively, the catalyst feed rate can be set to the value required to operate at full production once the second catalyst feed has begun. Method 2

The second method of operation, which can be applied to a catalytic solution, ensures that the two catalysts (and the co-catalyst(s)) are operated at the same time. This can be done if the correct reactor conditions for the desired product are known or if small variations in reactor conditions are not important for making the desired product. As in Method 1, if the kinetic parameters of the catalysts are known, the catalyst feed ratios when the reaction occurs can be adjusted to be according to specifications while keeping the reactor at its full production rate. Alternatively, the catalyst feed ratio can be set to the value required for operation at full production rate.

In a preferred embodiment, the reactor is operated with an LMW component to avoid gelation. The LMW component is then analyzed and conditions are adjusted to obtain the desired product. Then the HMW component begins to be fed. In general, a large amount of fines is produced due to the nature of the product, using a low molecular weight component. Raw fines can be analyzed to produce a feed hack that is faster than the finished product.

In a preferred embodiment, one or more methods may be used to alter the conditions to obtain the desired polymer properties in accordance with the methods described herein:

1) changing the amount of the first catalyst in the polymerization system, and/or 2) changing the amount of the second catalyst in the polymerization system, and/or 3) adding hydrogen to the polymerization process and/or changing the concentration of hydrogen in the system; wow

4) Changing the amount of liquid and/or gas withdrawn and/or purged from the process; wow

5) Changing the amount and/or composition of the recovered liquid and/or gas returned to the polymerization process, and recovering said liquid or gas from the polymer discharged from the polymerization process; and/or 6) the use of a hydrogenation catalyst in the polymerization process; and/or 7) changing the polymerization tempearture; and/or 8) changing the partial pressure of ethylene in the polymerization process; and/or 9) changing the ratio of ethylene to copolymer in the polymerization process; And/or 10) change the ratio of activator to transition metal in the activation sequence; wow

11) Changing the type of covalent monomer; wow

12) Change the activation time.

Once the desired polymer property of one catalyst is achieved during operation, feeding of another catalyst(s) and optional activator(s) can begin.

The methods of this invention may be used with any catalyst or catalytic system for olefin polymerization.

Catalysts and catalytic systems

The various catalysts or catalyst systems that may be used in this statement include metal compounds containing a group 15 element and/or phenoxide componds as described below. Other catalysts that can be used include transition metal catalysts not mentioned in the above description.

Such as a metallocene catalyst containing one or more bulky ligand metallocene-type and/or one or more conventional-type transition metal catalyst such as one or more Ziegler-Natta catalyst, one or more vanadium catalyst and/or chromium catalyst One or more chromium.

To achieve the purposes of this invention, the cyclopentadienyl group is defined to include indenyls and fluorenyls. A metal compound containing an element from group 15

The mixed catalyst composition according to the present invention comprises a metal compound containing an element of group 15. A compound containing an element from Group 15 usually includes a metal atom from Group 3 to Group 14, preferably from Group 3 to 7, preferably from Group 4 to 6, best of all a metal atom from Group 4, bound to an easily removable group. leaving at least one group that is further bonded to at least two atoms of group 15, at least one of which is further bonded to an atom of group 15 or 16 through another group.

In a preferred embodiment, at least one atom of group 15 is linked to an atom of group 15 or 16 through another group which may be a hydrocarbon group having from one to 20 carbon atoms, a group containing heteroatoms, silicon, germanium, Tin, lead, or phosphorus, where the atom of group 15 or 16 is not bonded to another atom or may be bonded to hydrogen, or to a group containing an atom of group 14, a halogen, or a group containing heteroatoms, and where each atom is also bonded. The two atoms of group 15 have a cyclic group, and each of them may optionally be bonded to a hydrogen, a halogen, a heteroatom, a hydrocarbyl group, or a group containing heteroatoms.

In a preferred embodiment, the metallic compound containing an element of group 15 according to the present invention may be represented by the following two formulas: Formula I

<img file="SA735B1_D0001.tif" />

Formula II

<img file="SA735B1_D0002.tif" />

M represents a transition metal from group 3 to 12 or one of the main metals of group 13 or 14, preferably a metal from group 4, 5 or 6, and the best is a metal from group 4, and the most preferred is zirconium, titanium or hafnium. Each A group that is easy to remove, preferably an anionic leaving group, preferably a hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and most preferably an alkyl, y, representing a value of 0 or 1 (when y is 0, it is The group 'L does not exist), n represents the oxidation state of M, preferably +3, +4, or +5, and preferably +4, m represents the formal charge of the ligand YZL or 'YZL, preferably zero, -1, -2 Or -3, or better -2,

L represents an element from group 15 or 16, preferably nitrogen.

L' represents an element from group 15 or 16 or a group containing an element from group 14, preferably carbon, silicon or germanium.

Y represents an element from group 15, preferably nitrogen, or phosphorus, preferably nitrogen.

Z represents an element from group 15, preferably nitrogen or phosphorus, preferably nitrogen.

R1 and R2 each separately represent a hydrocarbon group with one atom to, 2 carbon atoms, a group containing heteroatoms that includes no more than 20 carbon atoms, silicon, germanium, tin, lead or phosphorus, preferably an alkyl group, aryl or aralkyl, containing from two to two atoms. 20 carbon atoms, preferably a linear, branched, or cyclic alkyl group, C2-C20, and preferably a hydrocarbon group containing from two to six carbon atoms.

R3 is not present or represents a hydrocarbon group, hydrogen, halogen, a group containing a different atom, and preferably a linear, cyclic or branched alkyl group containing from one to 20 carbon atoms. It is preferable that R3 is not present, representing hydrogen or An alkyl group, most preferably representing hydrogen

R4 and R5 each represent an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted alkyl group, a cyclic aralkyl group, a cyclic aralkyl group, or a multiple system. Multiple ring system, preferably a group containing no more than 20 carbon atoms, and preferably between 3 and 10 carbon atoms; The best of all is a hydrocarbon group

A hydrocarbon with one to 20 carbon atoms, an aryl group C1-C20 C1-C20 aryl or an aralkyl group C1-C20 aralkyl C1-C20, or a group containing heteroatoms, for example PR3, where R represents an alkyl group. R1 and R2 bond to each other, and/or R4 and R5 may bond to each other, R6 and R7 may not be present, or they individually represent a hydrogen, an alkyl group, a halogen, a heteroatom, or a hydrocarbyl group. Preferably a linear, cyclic or branched alkyl group containing from one to 20 atoms. A carbon atom, and it is preferable that they do not exist, and *R does not exist, or represents hydrogen, a group containing an atom from group 14, and a halogen, a group containing different atoms.

The 'formal charge of the ligand YZL' or 'YZL&amp;' means the total charge of the ligand in the absence of the metal and the easily removed groups X.

What is meant by the phrase R1 and R2 may also be linked to each other is that R1 and R2 may be directly linked to each other or they may be linked to each other through other groups. What is meant by the phrase R4n and R5 may also be linked to each other, and that R4 and R5 may be directly linked to each other or they may be linked to each other through groups.

Other.

The alkyl group may be linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkyl radicals. thio alkylthio, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, aroylamino radicals

Alkylenes are linear, branched, cyclic, or a combination thereof. An aralkyl group is defined as an aryl group bearing substituents.

In a preferred embodiment, R4 and R5 are each individually represented by a combination of the following formula: Formula I

<img file="SA735B1_D0003.tif" />

where

R8 to R12 each individually represents a hydrogen, alkyl group C1-C40 C1-C40 alkyl, halide, heteroatom, group containing heteroatoms containing no more than 40 carbon atoms, preferably a linear or branched alkyl group It contains from one to 20 carbon atoms; A methyl, ethyl, propyl or butyl group is preferred, and any two of the R groups may form a cyclic and/or heterocyclic group. The ring groups may be aromatic. In a preferred embodiment, R9, R10 and R12 each individually represent a methyl, ethyl, propyl or butyl methyl group (including all isomers), and in a preferred embodiment R9, R10 and R12 represent methyl groups, and R8 represents And R11 hydrogen.hydrogen

In a particularly preferred embodiment, R4 and R5 represent a group in the formula

next:

Formula 2

<img file="SA735B1_D0004.tif" />

In this embodiment, M represents a group 4 metal, preferably zirconium,

Titanium or hafnium, and best of all zirconium; Z, Y, and L represent nitrogen; R1 and R2 represent the -CH2-CH2- cleft; R3 represents hydrogen; R6 and R7 are not present.

In a particularly preferred embodiment, the metallic compound containing an element from group 15 is represented by the following formula: Compound I

<img file="SA735B1_D0005.tif" />

In compound I, Ph refers to phenyl.

Metallic compounds containing elements of group 15 according to the invention are prepared using methods known in the art, such as those described in European Patent No. Al 454 893 0; US Patent No. 50,889,128 and references mentioned in US Patent No. 28, 5,889,1, all of which are mentioned in this statement for reference. U.S. Patent Application Serial No. 09/312,878, filed on May 17, 1999, and U.S. Patent No. 6,291,325 filed on August 7, 2001, describes a gas-phase or slurry-phase polymerization process using a portable bisamide catalyst, which They are also mentioned in this statement for reference.

A preferred direct synthesis method for these compounds involves the reaction of the neutral ligand (see for example ligand YZL or 'YZL' for formulas 1 or 2) with MnXn (m represents a group 3 to 14 metal, n represents the oxidation state of M, each an anionic group, such as a halide), in a non-coordinating or weakly coordinating solvent, such as ether, toluene' xylene, benzene, methylene chloride, and/or hexane or another solvent thereof boiling point point we want about 60°C, at a temperature ranging from about 0°C to about 150°C (preferably from 20 to 100°C), preferably for 24 hours or more, then treating the mixture with an excess amount (for example, four equivalents or more). ) of an alkylating agent, such as methyl magnesium bromide in ether. The magnesium salts are removed by filtration, and the metal complex is separated using standard techniques.

In an embodiment, the metal compound containing a group 15 element is prepared using a method comprising reacting a neutral ligand, (see for example ligand YZL or 'YZL of formulas 1 or 2) with a compound represented by the formula MnXn (where M represents a group 3 metal to 4 1, n represents the oxidation state of M, each

The temperature ranges from about 20 to about 100 C, then treating the mixture with an excess amount of alkylating agent, then extracting the metal complex. In a preferred embodiment the solvent has a boiling point greater than 60°C, such as toluene, xylene, and/or hexane. In another embodiment the solvent includes ether and/or methylene chloride, preferably ether.

A metallocene compound containing a bulky ligand

A metallocene compound containing a bulky ligand (also referred to hereinafter as metallocene compounds) may also be used in an application of this invention.

Typically, we include metallocene-type compounds containing a bulky ligand, generally half and full sandwich compounds containing one or more bulky ligands bound to at least one metal atom. Typical bulky ligand-containing metallocene-type compounds are generally described as containing one or more bulky ligand(s) and one or more easily eluted group(s) attached to at least one metal atom. In a preferred embodiment, at least one bulky ligand is η-bonded to the metal atom, and most preferably to the metal atom is an η-bonded etha bond at position 5

η5-bonded.

Macroligands are usually represented by one or more open, acyclic, or fused ring(s), one or more ring system(s), or a combination thereof. These large ligands, preferably the ring(s) or ring system(s), typically consist of atoms chosen from groups 13 to 16 of the Periodic Table of Elements, preferably from the group consisting of carbon, nitrogen, Oxygen, silicon, sulfur, phosphorus, germanium, boron, aluminum, or a combination thereof. It is most preferable that the ring(s) or ring system(s) be made of carbon atoms

Such as, but not limited to, cyclopentadienyl ligands, structures of cyclopentadienyl ligands, or other similar functioning ligand structures such as pentadiene, cyclooctatetraendiyl, or imide. It is preferable to choose the metal atom from groups 3 to 15 and the lanthanide or actinide series from the periodic table of the elements. It is preferable for the metal to be a transition metal, chosen from groups 4 to 12, preferably from groups 4, 5 and 6, and most preferably for the transition metal to be chosen from group 4.

In an embodiment of the invention, metallocene catalytic compounds containing a bulky ligand are represented by the formula:

III) LALbmqn)

Where M represents a metal chosen from the periodic table of elements. It may be chosen from groups 3 to 12 or from the lanthanide series or actinide from the periodic table of elements. It is preferable that M represents a transition metal from group 4, 5 or 6, and it is preferable that M represents a transition metal. Of group 4, M would ideally represent zirconium, hafnium, or titanium. The bulky ligands, LA and LB, represent ring(s) or ring system(s), open, acyclic or compact, and any ancillary ligand system, including cyclopentadienyl ligands with or without substituents or pentadienyl ligands. Cyclopentadienyl, cyclopentadienyl ligands bearing heteroatom substituents and/or cyclopentadienyl ligands containing a heteroatom. Examples of bulky ligands include, but are not limited to, cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, ligands

octahydrofluorenyl, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands pentalene ligands, ligands

phosphoyl, phoshinimine ligands (see international patent application

No. 99/40125), pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, such as terahydroindenyl ligands. In an embodiment, LA, LB, and any other ligand structure having the ability to bind to M may represent an eta bond, preferably binding to M an eta bond at position 3 and most preferably at position 5. In yet another embodiment, the atomic molecular weight (MW for La or LB) exceeds 60 atomic molecular units (amu), preferably greater than 65 atomic mass units. In another embodiment, La or LB may contain one or more heteroatoms, for example nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination with carbon atoms to form an open, acyclic ring, or preferably Incorporated or ring system, for example, an additional cyclopentadienyl ancillary ligand containing a hetero-cyclopentadienyl ancillary ligand. Other bulky La or LB ligands include, but are not limited to, bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins, and other macrocyclic polyazomacrocycles. . Each La or LB are individually identical or different types of a bulky ligand bound to M. In an embodiment according to formula (III) there is only one La or LB ligand.

Independently, both A and A may have or lack substituents from some combination of substituent R groups. Examples of R substituents include, but are not limited to, one or more hydrogen-selected groups, linear or branched alkyl radicals, alkenyl radicals, alkynyl radicals, cycloalkyl radicals, aryl radicals, or acyl radicals. Aroyl radicals, alkoxy radicals, aryloxy radicals, alkylhio radicals, dialkylamino radicals

alkoxycarbonyl aryloxycarbonyl radicals, aryloxycarbonyl radicals

Carbamoyl, alkyl or dialkyl carbamoyl, acyloxy, acylamino, or straight, branched or cyclic alkylene, or a combination thereof. In a preferred embodiment, the substituent R groups contain no more than 50 non-hydrogen atoms, preferably from one to 30 carbon atoms, which may also contain substitutions of halogens, heteroatoms, or the like. Examples of alkyl substituents R include, but are not limited to, methyl groups, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, benzyl or phenyl and the like, including all Its counterparts, for example tertiary butyl, isopropyl, and the like. Other hydrocarbyl radicals include organometalloid radicals bearing a substituent of fluoromethyl, fluroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyls including trimethylsilyl, tamethylgermyl, and trimethylgermyl Diethyl methyldiethylsilyl silyl and the like; Semi-metallic organic moieties bearing a halocarbyl substituent, including tri(tert methyl-bis(difluoromethyl)silyl, tris(trifluoromethyl)-silyl, bromomethyldimethylgermyl and the like; substituted boron moieties, including dimethylboron, for example; And apartments

Bi-substituted pnictogen including dimethylamine, dimethyl

dimethylphosphine, diphenylamine, methylphenylphosphine

methylphenylphosphine, chalcogen moieties including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethyl sulfide. Non-hydrogen R substituents include carbon atoms

Silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like, including but not limited to olefins Olefinically unsaturated substituents including terminal ligands Vinyl-terminated ligands, eg but-3-enyl, prop-2-enyl, hex-5-enyl and the like. Likewise, at least two groups of R, and preferably two adjacent groups of R, are linked to form a ring sfructure structure containing from 3 to 30 atoms chosen from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, Boron or a combination thereof. Also, a substituted R group such as l-butanyl may form a carbon sigma bond with the metal M.

Other ligands may bind to the transition metal, such as at least one easily eluted group symbolized by Q. In an embodiment, Q represents an unstable monoanionic labile ligand containing a sigma bond with M. Depending on the oxidation state of the metal, the value of n is zero, 1 Or 2, so that formula (III) above represents a metallocene catalytic compound containing a bulky neutral ligand.

Examples of Q include, but are not limited to, weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl moieties containing from one to 20 carbon atoms, carbon hydrides, halogens, and the like. A combination thereof. In another embodiment, two or more Q-ligands may form part of a compact ring or ring system. Other examples of Q ligands include those substituents for the R moiety described above and include cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy. propoxy, phenoxy

phenoxy, bis(N-methyl anilide), dimethylamide, dimethylphosphide and the like.

The two groups L may be bridged to each other via group A, as will be known below.

In an embodiment, the metallocene catalyst compounds containing a bulky ligand according to the invention include those compounds of formula (III) wherein La or LB are bridged to each other by means of at least one bridging group, A, such that formula B represents:

iv)LaALbMQn)

These bridged compounds, represented by formula (IV), are known as metallocene bridge catalytic compounds containing a bulky ligand. LB, LA, Q, M and n are played as mentioned above. Examples of bridge group A include, but are not limited to, bridge groups containing at least one atom from group 3 1 through 16, often referred to as a divalent moiety, such as but not limited to at least one atom of carbon, oxygen, Nitrogen, silicon, aluminum, boron, germanium, tin, or a combination thereof. Preferably, the bridge group A must contain a carbon atom, silicon, or germanium, and most preferably, the bridge group A must contain at least one silicon atom or at least one carbon atom. The bridge group A may also contain alternative R groups as defined above, including halogens and iron. Examples of bridge group A may be represented, but not limited to, by R'2Si, R'2C, R'P, R'2Ge, R'2SiR'2Si, where 'R' represents each individual radical group representing a hydride, a hydrocarbyl. hydrocarbyl, hydrocarbyl bydrocarbyl with substituents, halocarbyl, halocarbyl with substituents, semi-metallic organic compound with a hydrocarbyl substituent hydrocarbyl, semi-metallic organic compound with a halocarbyl substituent, halocarbyl

A di-substituted boron, a di-substituted pnictogen, a chalcogen carrying substituents, or a halogen. Two or more 'R' groups may be linked to form a ring or ring system. In one embodiment, the metallocene catalyst compounds include: On a bulky ligand which is bridged by formula (IV) on two or more bridge groups A (see European Patent No. Bl 301 664).

In an embodiment, the metallocene catalytic compounds containing a bulky ligand include those compounds where the R substituents on the La or LB bulky ligand in forms (III) and (IV) carry a similar or different number of substituents on each of the bulky ligands. In another embodiment, the bulky ligands La or LB in forms (III) and (IV) are distinct from each other.

Other metallocene catalyst compounds containing a bulky ligand and catalytic systems useful in the invention include those described in U.S. Patent Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, and 5 5,276,2.8 854,363, 5,856,547, 5,858,903, 5,859,158, 517, 5,900 and 503,939.5, and PCT International Patent Bulletins Nos. 93/08221, 93 /08199 07140/95, 98/11144, 8/41530, 98/41529, 98/46650, 99/02540, 4221 99/1, and European Patent Publications Nos. 838 0578-A, 595 638 .-A, 380 513 0-B, 372 816 0-A1, 834 839 0-A2. , 819 632 0-B1, 821 748 0-B2 and 996 757 0-B1, all of which are mentioned in this statement in full for reference.

In an embodiment, other catalyst compounds of the metallocene type containing a bulky ligand suitable for use in this invention include bridge compounds of the metallocene type containing a heteroatom, a mono-bulky ligand. Examples of these catalytic types and catalytic systems have been described in the literature

International Patent Cooperation Treaty Patent Nos. 00333/92, 94/07928, 42570/91, 35060/94, 02440/96, 97/15602 and 99/20637

and U.S. Patent Nos. 475,057.5, 867,096,5,438,055.5, 5,198,401, 05,227.44 and 405,264,405 and European Patent Publication No. 436,420 0-A, all of which are fully incorporated herein by reference.

In this embodiment, the metallocene catalytic compound containing a bulky ligand is represented by the formula:

V)LcAJMQn)

Where M represents a metal atom from groups 3 to 16 or a metal chosen from the group that consists of the actinides and lanthanides of the periodic table of elements. It is preferable that M represents a transition metal from groups 4 to 12, and it is preferable that M represents a transition metal from groups 4, 5 or 6, and it is most preferable that M represents a group 4 transition metal in any oxidation state, particularly titanium; Lc represents a bulky ligand with or without substituents attached to M; J is linked to M; M is linked to A and J, and J represents an additional heteroatom ligand; And A lives gantry set; Q represents a univalent anionic ligand; n represents an integer equal to zero, 1 or 2. In formula (V) above, LC, A and J form a compact ring system. In an embodiment, L is in the form (V) as defined above for LA and LA, A, M and Q are in the form (V) as defined above in the form (III).

In formula (v), J represents a bond containing a heteroatom, where J represents an element with a coordination number of 3 from group 15 or an element with a coordination number of 2 from group 16 of the periodic table of elements. Preferably, J should contain a nitrogen atom, phosphorous, oxygen or sulfur, and preferably nitrogen.

nitrogen

In one embodiment according to the invention, metallocene catalyst compounds containing a bulky ligand are composites of a mixed cyclic ligand

heterocyclic ligand complexes where we include the bulky ligand, the ring(s) or ring system(s), one or more heteroatoms or a combination thereof. Examples of heteroatoms include, but are not limited to, elements of groups 13 to 16, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorous, and tin. Examples of metallocene catalyst compounds containing this bulky ligand are described in International Patent Applications Nos. 02 96/332, 96/34021, 97/17379 and 98/22486, European Patent No. 0874005-A1, and US Patent Nos. 05,637. 66, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417 and 5,856,258, all of which are mentioned in this statement for reference.

In an embodiment, metallocene catalyst compounds containing a bulky ligand include those known as transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, such as those described in U.S. Patent Application Serial No. 103,620/09. Filed on June 23, 1998, US Patent No. 601,030,657, filed on August 15, 2000, which is mentioned in this statement for reference. In another embodiment, metallocene catalyst compounds containing a bulky ligand include compounds described in PCT international patent applications Nos. 99/01481 and 98/42664, which are set forth in this statement in full by reference .

In a preferred embodiment, the catalytic compound is of the metallocene type having a bulk ligand that is a complex of a metal, preferably a transition metal, a bulk ligand, preferably a pi-bonded ligand with or without substituents, and one or more heteroallyl moieties. , such as those described in US Patent Nos. 505270752

and 5,747,406 and European Patent No. 57 0 735 0-Bl, all of which are incorporated herein by reference.

In a particularly preferred embodiment, the other metal or dimetallic compound is the catalytic compound of a type. metallocene, which contains a bulky ligand, which is represented by the formula:

VI)LDMQ2(YZ)Xn)

Where M represents a metal from groups 3 to 16, preferably a transition metal from group 4 to 12, and most preferably a transition metal from groups 4, 5 or 6; L represents a bulky ligand bound to M; Each Q is individually bound to M and forms a ligand (Q2(YZ), preferably a unicharged polydentate ligand; A or Q represents a monovalent anionic ligand also bound to M;

And X represents a monovalent anion group when n equals 2, or X represents a divalent anion group when n equals 1; n represents a value of 1 or 2.

And in the formula (L) (VL and M) as defined above for formula (III). And Q is as defined above for formula (III), and it is preferable to choose Q from the group that consists of -O-, -CR2-, -nr- and -S-; Y represents C or S; Z is chosen from the set consisting of SR, -CR3, -NR2, -OR-, H, -PR2, -SiR, -, and aryl groups with or without substituents, provided that when Q represents -NR-, Z chooses from The group consisting of PR2,-SiR3,-SR,_NR2,-OR- and neither-; R is chosen from a group containing carbon, silicon, nitrogen, oxygen, and/or phosphorous, and R preferably represents a hydrocarbon group. Contains from one to 20 carbon atoms, most preferably an alkyl, cycloalkyl, or aryl group; n represents an integer ranging from 1 to 4, preferably 1 or 2; X represents a monovalent anionic group when n equals 2 or X represents a divalent anionic group when n equals 1;

Preferably, X represents a carbamate, carboxylate, or other heteroallyl moiety described by the combination of Z and Y, Q.

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

<img file="SA735B1_D0006.tif" />

Phenoxide Catalysts

Another group of catalysts that may be used in the process of this invention includes one or more catalysts represented by the following two formulas:

<img file="SA735B1_D0007.tif" />

or

Where R1 represents hydrogen or a group containing from 4 to 100 carbon atoms, preferably a tertiary alkyl group, preferably a C4-C20 alkyl group, preferably a tertiary alkyl group containing from 4 to 20 carbon atoms, preferably A neutral group containing from 4 to 100 carbon atoms, which may or may not be bonded to M. At least one radical from R2 to R5 represents a group containing a heteroatom, and the rest of the radicals from R2 to R5 each represent a separate hydrogen or a group containing atom to 100 carbon atoms, The C4-C20 alkyl group is preferred (preferably butyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl, nonyl, dodecyl) and any of the moieties may be linked. R2 to R5 are also associated with M or may not be associated with M,

0 Oxygen, M represents a transition metal from group 3 to 01 or lanthanide, preferably a metal from group 4, preferably Zr, Ti or Hf; n represents the valence state of the metal M, preferably 2, 3, 4 or 5, and Q represents an alkyl group, a halogen, a benzyl, an amide, a carboxylate, a carbamate, a thiolate, a hydride, an alkoxide, or a bond. For a group R containing a heteroatom, it may be any of the slits from R1 to R5, and the group containing a heteroatom may be any heteroatom. Or a heteroatom bonded to carbon silica or another heteroatom. Favorite heteroatoms include boron, aluminum, silicon, nitrogen, phosphorous, arsenic, tin, lead, antimony, oxygen, selenium, and tellurium. Particularly favored heteroatoms include nitrogen, oxygen, phosphorous, and sulfur. The best heteroatoms include, in particular, oxygen and nitrogen. The heteroatom itself may be directly linked to a ring

Phenoxide, or it may be attached to another atom or atoms linked to the phenoxide ring. A group containing a heteroatom may include one or more identical or different heteroatoms. Connect groups of heteroatoms

Preferred are imines, amines, oxides, phosphines, ethers, ketenes, heterocyclics, oxazolines, thioethers and the like. Particularly favored heteroatom groups include imines. Any two adjacent R groups may form a ring structure.

A five-membered or six-membered ring is preferred. Likewise, R groups may form multi-ring structures. In an embodiment, any two or more R groups do not form a five-membered ring.

These phenoxide catalysts may be activated using activators including alkyl aluminum compounds (such as diethylaluminum chloride), alumoxanes, modified alumoxanes, non-coordinating anions, Group 13 metal anions, or metalliod anions. Asymmetric anions, boranes, borates, and the like. For more information about stimulants, see the Steroids section below.

Conventional type transition metal catalysts

Conventional type transition metal catalysts include Ziegler-Natta, vanadium, and Phillips catalysts that are well known in technology. Such as, for example, Ziegler-Natta catalysts described in the book Ziegler-Natta Catalysts and Polymerizations, by John Boor, Academic Press, New York City, 1979. Examples of conventional type transition metal catalysts are described in US Patent Nos. 5,639 1 4.1, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879, 359 and 4,960,741,

All of which are fully incorporated into this statement for reference. Conventional type transition metal catalyst compounds that may be used in this present invention include transition metal compounds from groups 3 to 17, preferably 4 to 12, and preferably 4 to 6 of the periodic table of chemical elements.

These transition metal catalysts of the traditional type may be represented by the formula: MRx, where M represents a metal chosen from the metals of groups 3 to 17, preferably from the metals of group 4 to 6, the best of the metals of group 4, and the most preferred is titanium; And R represents a halogen atom or a hydrocarbyloxy group. And X represents the oxidation state of the metal M. Examples of R include but are not limited to alkoxy, phenoxy, and bromide. bromide, chloride and fluoride. Examples of conventional type transition metal catalysts, where M represents titanium, include, but are not limited to, TiCl4.

Ti(OC2,H5)2Br2, Ti(OC3H7)2Cl2, Ti(OC4H9)3Cl, Ti(OC2H5)Cl3, Ti(OC2H5)3Cl, TiBr4' TiCl3.l/3AlCl3 and H25)Cl3Ti(OC12)

Conventional transition metal catalyst compounds based on electron-donor complexes of titanium/magnesium suitable for use in this invention have been described, for example, in U.S. Patents Nos. 40,302,565 and 4,302,566, which are incorporated herein. The full statement is for reference. The 4 derivative (ethyl acetate) MgTiCl6 is particularly preferred.

UK Patent Application No. 05,355 2.1 and US Patent No. 36 0 7, 5.31 describe various conventional catalytic compounds containing vanadium, which are incorporated herein by reference. Examples of conventional catalyst compounds containing vanadium include, but are not limited to, vanadyl trihalide, vanadyl alkoxy halides, and vanadyl alkoxides such as VOCl2(OBu), VOC13, where Bu represents butyl, VO(OC2H5)3. ; Vanadium tetra-halide and vanadium alkoxy halides, such as

VCl3(OBu) and VCI4; Vanadium and vanadyl acetyl acetonates, and chloroacetyl acetonates such as 3(V(AcAc) and (VOCI2(AcAc), where (AcAc) represents acetyl acetonate. Preferred conventional vanadium catalyst compounds include VOCl2-OR and VCI4, VOCI3, where R represents a hydrocarbon radical, preferably an aliphatic or aromatic hydrocarbon radical containing one to 10 carbon atoms, such as ethyl, phenyl, isopropyl, butyl. Propyl, n-butyl, isobutyl, tertiary-butyl, hexyl, cyclohexyl, naphthyl. Etc., and vanadium acetyl acetonates.

Examples of conventional chromium catalyst compounds, often referred to as Phillips-type catalysts, suitable for use in the present invention include CrO3, chromocene, silyl chromate, chromyl chloride (CrOzClz), 2-ethyl chromium hexanoate chromium-2-ethyl-hexanoate,

Chromium acetylacetonate (Cr(AcAch)) (Cr(AcAc), and the like. Unspecified examples are described in US Patent Nos. 9,853 0 3.7, 3,709,954, 3,231 ,550, 3,242,099 and 4,077,904, which are incorporated herein by reference.

Other conventional type transition metal catalyst compounds and catalytic systems suitable for use in this invention are described in U.S. Patent Nos. 401240532, 4,302,565, 4,302,566, 4,3760.62, 4,379,758, 5, 066,737, 50,763,723, 5,849,655, 44 5,852.1, 5,854,164 and 5,869,585 and the two European patent publications A2 416815 0 A2 and 436 420 0 Al, all of which are incorporated In this statement for reference.

Other catalysts may include cationic catalysts such as AICI3, and other catalysts of cobalt, iron, nickel and palladium are well known in

Technology - See, for example, U.S. Patent Nos. 3,487,112, 4,472,559, 4,182,81, and 4,689,437.4, all of which are incorporated herein by reference.

to it for reference.

Typically, these conventional type transition metal catalyst compounds, with the exception of some conventional chromium catalyst compounds, are activated using one or more of the conventional co-catalysts described below. Conventional type co-catalysts

Covalent catalyst compounds of a conventional type may be represented by transition metal catalyst compounds of a conventional type shown above with the formula M3 M4 vX2 cR3 bc, where M3 represents a metal selected from the metals of groups 1 to 3 and 12 to 13 of the periodic table of elements; M4 represents a group 1 metal of the periodic table of elements; V represents a number equal to 0 or 1; Each X2 represents any halogen atom; c represents a number ranging from 0 to 3; Each R3 represents a monovalent hydrocarbon moiety. or hydrogen; b represents a number ranging from 1 to 4; Where b minus C equals at least 1. The compounds of organometallic cocatalysts of the traditional type and the other transition metal catalysts of the traditional type mentioned above are represented by the formula M3R3k, where M3 represents a metal chosen from the metals of groups IIB, IIA, 1A or IIIA, such as lithium, sodium, beryllium, barium. barium, boron, aluminum, zinc, cadmium and gallium; k is equal to 1, 2 or 3, based on the M3 valency which in turn usually depends on the specific set in which M3 belongs to it; Each R3 represents a monovalent hydrocarbon radical.

Examples of conventional-type organometallic cocatalysts that are suitable for use with the conventional-type catalytic compounds described above include, but are not limited to, methyllithium, butyllithium, dihexylmercury, butylmagnesium, diethiylcadmium,

benzylpotassium, diethylzinc, tri-n-butylaluminum diisobutyl ethylboron, diethyl

Dietbylcadmium cadmium, di-n-butylzinc and tri-n-amylboron, and in particular, aluminum alkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylaluminum and triisobutyl Aluminum triisobutylaluminum Other conventional co-catalyst compounds include mono-organohalides, hydrides of Group 2 metals, and mono- or di-halides

Di-organohalides and hydrides of group 3 and 13 metals. Include

Examples of conventional catalytic compounds of this type include, but are not limited to, di-isobutlaluminum bromide, diisobutyl chloride.

Isobutylboron dichloride, methyl magnesium chloride, ethylberyllium chloride, ethylcalcium bromide, di-isobutylaluminum hydride, methylcadmium hydride, diethylboron hydride, HC hydride Silberyllium hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride, butylzinc hydride, Dichloroboron hydride, di-bromoaluminum hydride, and bromocadmium hydride. Conventional organometallic co-catalyst compounds are well known to those familiar with the technology, and a fuller description of these compounds is provided in US Patent Nos. 3,221,002 and 50930415, which are fully incorporated herein by reference. Steroids

The catalysts, preferably a compound containing an element from Group 15 and/or the metallocene catalysts described in this statement, are preferably mixed with one or more activators.

To form catalyst systems for olefin polymerization. Preferred activators include alkyl aluminum compounds (such as diethylaluminum chloride), alumoxanes, modified alumoxanes, chiral anions, group 13 metal anions or chiral metalliod anions, boranes, compounds Borates and the like. It is considered within the scope of the present invention to use alumoxanes or modified alumoxanes as an activator, and/or also use ionizing activators, neutral or ionic.

ionic, such as tri-(p-butyl)ammonium quaternary(pentafluorophenyl)boron

Tri(n-butyl) ammonium tetrakis (pentafluorophenyl) boron or a semi-metallic precursor source of trisperfluorophenyl boron ionizes the neutral metallocene compound. Other useful compounds include triphenyl boron, triethyl boron, tri-n-butyl ammonium tetraethylborate, triaryl borane, and the like. Other useful compounds also include aluminate salts

In a detailed embodiment the modified alumoxanes are mixed with catalysts to form a catalytic system. In a preferred embodiment, MMAO3A (methyl alumoxane modified in heptane, commercially available from Akzo Chemicals, Inc.) is mixed with the trade name Modified Methylalumoxane type 3A, which is protected in US Patent No. 5 ,041,584) 0p the first and second metallic compounds to form a catalytic system.

There are several methods for preparing alumoxanes and modified alumoxanes, and examples of these methods are described, but are not limited to, in US Patent Nos. 08 4,665.2, 4,952,540, 5,091,352, 5,206,199. , 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5 ,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,

5,041,584, 5,693,838, 355,731.2, 5,041,584 and 5,731,451 and European Patent Publications Nos. 476,561 0-A, 586 279 0-B1, 218 594 0-A The international patent application pursuant to the Patent Cooperation Treaty No. 94/10180, all of which are mentioned herein for reference.

Ionizing compounds may contain an active proton or another cation associated with the remaining ion in the ionized compound, but not coordinated to it, or only loosely attached to it. Compounds of this and similar types are described in European Patent Publications Nos. 982 570 0-A, 732 520 0-A, 495 375 0-A, 637 426 0-A, 944 003 277 0-A, 277 004 0. -A, US Patent Nos. 57 53.1 5.1, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,387,568, 5,384,299 , 5,502,124 and 5,643,847, all of which are mentioned in this statement for reference. Other stimulants include those described in the International Patent Publication pursuant to Patent Cooperation Treaty No. 98/07515 such as tris(2,2',2'-nonafluorobiphenyl) and trisfluoroaluminate (2,2',2''-nonafluorobiphenyl). ) fluoroaluminate, which is mentioned in this statement for reference. The invention further includes combinations of activators, for example, alumoxanes and ionized activators in combinations, for example see Patent Cooperation Treaty International Patent Publications Nos. 94/07928 and 95/14044 and US Patent Nos. 57 5301 501 And 5,453,410, all of which have been mentioned in this statement for reference. To achieve the purposes of this invention, stimulation methods such as radiation and the like may also be used.

When two different catalysts are used, the first and second catalyst compounds can be mixed in molar ratios ranging from 1:1000 to 1000:1, preferably 99:1 to 99:1, preferably 90:10 to 90:10, preferably 80:20. to 20:80, best from 30:70 to 70:30, best from 60:40 to 40:60. The specific ratio chosen depends on the product

Desired endpoint and/or activation method. A practical way to determine the best ratio to obtain the desired polymer is to start with a 1:1 ratio, measure the desired property of the product formed and adjust the ratio accordingly.

In a particular embodiment, when using compound I and indenyl zirconium tris-pivalate where both are activated using the same activator, the preferred weight percentages, based on the weight of the catalysts, not the activator or any support, range from 10 to 95%. by weight of compound I and 5 to 90% by weight of indenyl zirconium tris-pivalate, preferably 50 to

90% by weight of Compound I and 10 to 50% by weight of indenyl zirconium tris-pivalate, preferably 60 to 80% by weight of Compound I and 20 to

40% by weight of indenyl zirconium tris-pivalate. In a particularly preferred embodiment, indenyl zirconium tris-pivalate is activated with methylalumoxane, then mixed with compound I and the mixture is injected into the reactor.

Multi-component catalyst systems with similar activity and/or decay rates provide a route for olefin polymerization where the effects of the residence time of the catalyst in the reactor can be mitigated. Preferably, the catalysts should have a decay rate similar to that measured by a decay model, being first order or higher. Preferably, the decay rates, or alternatively, the half-lives of the catalysts, should vary by about 40% of each other, preferably about

20% apart, and the most preferable range is from about 10 to 0% apart. Zero% means they are essentially the same. The decay constant (Kd) is measured by running the reactor at set conditions, stopping the catalyst feed, but with all other feed streams continuing. The reactor is then allowed to reach equilibrium. During this time period the bed builds up and a graph is obtained. plot for bed weight

Against time. Assuming that the decay behavior is first-order, the decay constant is calculated. If two or more catalysts are to be compared, the procedure described above is repeated using exactly the same reactor conditions.

It is recognized that decay characteristics may be affected by temperature.

Monomer pressure, type and concentration of co-monomer, hydrogen concentration, additives/modifiers/other catalysts, catalyst poisons or impurities in the gas stream, presence of condensing agents or operation in condensing mode.

The natural consequence of this is that one or both of the catalysts will have a rapid decay rate such that they will be relatively insensitive to the effects of residence time in the normal range for reactor operation. It is possible to calculate the extent to which decay rates differ between catalysts based on their respective decay rates, so that the change in polymeric properties in the reactor is relatively small when there are changes in residence time.

In another embodiment, the first catalyst is chosen because when used alone it produces a polymer having a high average molecular weight (such as, for example, higher than 100,000, preferably higher than 150,000, preferably higher than 200,000, preferably higher than 250,000, and preferably higher than 300,000). The second catalyst is chosen because when it is used alone, it produces a polymer that has a low molecular weight (such as, for example, less than

80,000, preferably less than 7,0000, preferably less than 60,000, preferably less than 50,000, preferably less than 40,000, preferably less than 30000, preferably less than 20,000 and above

5000, better less than 20000 and higher than 10000).

In a preferred embodiment, a second catalyst produces a polyolefin that has a lower molecular weight than the polyolefin produced by the first catalyst when they polymerize independently in identical systems.

When three or more catalysts are used, the polymerization split can be estimated using multi-component catalysts and controlled by perturbing the feed rate of one or both of the catalysts when fed to the polymerization reactor and measuring the change in the polymer production rate. The invention is particularly useful when the catalysts are indistinguishable elementally but can be used with other systems. The invention is particularly applicable to systems where the relative amounts of each catalyst can be changed, for example to feed a solution or feed a hybrid solution.

The change in the catalyst feed rate is less than 40%, preferably less than 15% and most preferably about 5 to 10%. There are companying changes in the polymer split composition, but they are very small and may not be significant since the time-frame for observing changes in production rate may be short relative to the residence time in the reactor. It reduces the change in the polymer structure.

There is no need to draw the production rate, but it can be estimated mathematically when it ranges from about 30 to 80% of its final value depending on the theoretical response of the CSTR (continuous stirred tank reactor) to a step change.

The simplest case is a catalyst with a very fast decay rate so that the effects of residence time are not important (although decay can easily be dealt with using a simple formula). As an example, catalysts A and B were fed at a ratio of 50:50, yielding 10,000 pph of resin, then by increasing catalyst A by 10% and keeping the ratio B constant so that the feed stream split was at a ratio of 55:50. The production rate increased from 10000 to 10500 hecto parts. The difference of 5000 hecto is due to a 10% increase in catalyst A, so the initial amount of resin produced by catalyst A was 0 0 0 5 hecto and its new value is 5500 hecto. It was rate

The initial polymer split 50:50 and its new split rate was 50:55 (in this example the two catalysts were equally effective but the equation can be applied to other systems).

The feed rate of the catalyst or one or both of the catalysts can be perturbed constantly by small amounts around the intended split rate (more or less), so that the overall resin composition is always around the intended split rate. A gradual change is obtained and the response is measured. System performance may include a new term based on the measured split rate to explain changes in catalyst yield and decay.

Catalyst productivity models can be used, including the effects of temperature, residence time, monomer partial pressure, type and concentration of co-monomer, hydrogen concentration, impurities, inerts such as isopentane, and/or operation at or near condensation for each It consists of a multi-component separate addition polymerization system to control the polymerization fraction. In response to changes in changes, the feed rates of the component catalysts can be adjusted. For example, a change in residence time can be compensated for by forward control, which automatically adjusts catalyst feed rates to a new target value. The effects of temperature, partial pressure and other variables can also be compensated for with a feed-forward control method.

Models can also be used to control a process based on the measured polymer splits. For example, the partial pressure of ethylene can be adjusted by models based on the measured cleavage. It is also possible to adjust the concentration of an inert material that affects the productivity of one catalyst more than another (such as isopentane due to its potentially tempered cooling effect).

More generally, catalyst feed rates can be adjusted to return the measured polymer cleavage to the target cleavage. The effects of catalyst decay and residence time are part of...

model, thus controlling the equal use of even catalysts that have significant or different decay rates.

The present invention can be applied to gas-phase polymerization using a solution or liquid feed stream.

In general, the combined catalysts and the activator are mixed in proportions ranging from about 1:1000 to about 0.5:7. In a preferred embodiment, the catalysts and the activator are mixed in a proportion

It ranges from about 1:300 to about 1:1, preferably from about 150:1 to about 1:1, for boranes, borates, aluminates, etc. It is preferable that the ratio range from about 1:1 to about 1:10, and for alkyl aluminum compounds (such as diethylaluminum chloride mixed with water) it is preferable that the ratio range from about 1:0.5 to about 1:10.

It is preferable that the catalysts be produced in molar ratios ranging from 1000:1 to 1:1000, preferably from 99:1 to 1:99, preferably from 90:10 to 10:90, preferably from 80:20 to 20:80, preferably from 70: 30 to 30:70, better 40:60 to 40:60. The specific ratio chosen depends on the desired final product and/or activation method. A practical way to determine the best ratio to obtain the desired polymer is to start with a 1:1 ratio, measure the desired property in the product formed and adjust the ratio accordingly.

In a particular embodiment, when using compound I and zirconium tris-pivalate where both are activated using the same activator, the preferred weight percentages, based on the weight of the catalysts, not the activator or any carrier, range from 10 to 95% by weight of compound I and 5 to 90% by weight of zirconium tris-pivalate, preferably 50 to 90% by weight of compound I and 10 to 50% by weight of zirconium tris-pivalate, preferably 60% to 80%. by weight of compound I and from 40 to 20% by weight Of zirconium tris-pivalate. In a particularly favorite embodiment it is active

zirconium tris-pivalate using methylalumoxane, then mixing it with compound I and injecting the mixture into the reactor.

It is preferable to add the catalysts and activator to a slurry or gas phase reactor in a liquid carrier, preferably in solution. The catalyst and activator may be fed separately or together and may be mixed immediately before being placed in the reactor or may be contacted for longer periods of time before being placed in the reactor. Carriers may include any liquid that does not severely affect the effectiveness of the catalysts. The preferred liquid carriers are alkanes, preferably propane, butane, isobutane, pentane, hexane, xylene, heptane, toluene, cyclohexane, isopentane, octene or combinations thereof, and include particularly preferred carriers. Isopentane and/or hexane.

It is preferable to add the catalytic system, catalysts and/or activator to the reactor in one or more solutions. In one embodiment, a solution of an alkane-activated metal compound such as pentane, hexane, toluene, isopentane or the like is added to a gas-phase or slurry-phase reactor. In another embodiment the catalytic system or components thereof may be added to the reactor in a suspension or emulsion. In an embodiment, the transition metal compound is brought into contact with an activator, such as modified methylalumoxane, in a solvent immediately before the solution is fed to a gas-phase or slurry reactor. In another embodiment, a solution of the metal compound is mixed with a solution of the activator, the reaction is allowed to occur for a period of time and then the resulting mixture is added to the reactor. In a preferred embodiment, the catalyst and activator are allowed to react for at least 120 minutes, preferably at least 60 minutes and ideally between 1 and 30 minutes, before being added to the reactor. The catalyst and activator are usually found at a concentration of about 0.10 mol/L or less in solutions, preferably about 0.5 mol/L or less, preferably about 0.02 mol/L, and preferably ranging from about 0.10 to About 0.01 mol/L.

Catalyst solutions are prepared by selecting the catalyst and dissolving it in any solvent such as alkane.

Toluene, xylene, etc. The solvent may first be purified to remove any toxins that may linger

on the effectiveness of the catalyst, including any trace amounts of water and/or oxygenated compounds. The solvent may be purified using, for example, activated alumina and/or a portable copper catalyst. It is preferable that the catalyst be completely dissolved in the solution to form a homogeneous solution. Both the catalyst and activator may be dissolved in the same solvent, as desired. Once the catalysts are in solution, they may be stored for an indefinite period of time until they are used.

For the polymerization process, it is preferable to mix the catalyst with the activator before injection into the reactor. In addition, solvents and other reactants may be added to the catalyst solutions (on-line or off-line), to the activator (on-line or off-line), to the catalyst or activated catalysts.

The skill index (and/or other properties) of the resulting polymer can be varied by modifying the polymerization system by:

1) Increasing the amount of the first catalyst in the polymerization system, and/or

2) Changing the amount of the second catalyst in the polymerization system, and/or

3) Adding hydrogen to the polymerization process; wow

4) Changing the amount of liquid, gas and/or detergent withdrawn from the process; wow

5) Changing the amount and/or composition of the extracted liquid and/or extracted gas returned to the polymerization process, such that said extracted liquid or extracted gas is recovered from the polymer released from the polymerization process; wow

6) Using a hydrogenation catalyst in the polymerization process; wow

7) Changing the polymerization temperature; wow

8) Changing the partial pressure of ethylene in the polymerization process; and/or 9) changing the ratio of ethylene to the copolymer in the polymerization process; and/or 10) changing the ratio of activator to transition metal in the activation sequence;

wow

1 1) Changing the type of covalent monomer; And/or 2 1) Changing the activation time of the catalyst.

In an embodiment, the hydrogen concentration in the reactor ranges from about 200 to 2000 ppm, preferably from 250 to 1900 ppm, preferably from 300 to 1800 ppm, preferably from 350 to 1700 ppm, preferably from 400 to 1600 ppm Per million, preferably 500 to 1,500 ppm, preferably from

500 To 1400 ppm, preferably 500 to 1200 ppm, preferably 600 to 1200 ppm, preferably 700 to 1100 ppm, preferably 800 to 1000 ppm.

In another embodiment, the first catalyst is chosen because when used alone it produces a polymer having a high average molecular weight (such as, for example, above 100,000, preferably above 150,000, preferably above 200,000, preferably above 250,000, and preferably above 300,000) and the second catalyst is chosen. Because when used alone, it produces a polymer that has a low molecular weight (such as for example less than 80,000, preferably less than 70,000, preferably less than

60,000, the best is less than 50,000, the best is less than 40,000, the best is less than 30,000, the best is less than 20,000 and higher than 500, the best is less than 20,000 and higher than 10,000).

The blended catalysts and activator are generally mixed in ratios ranging from about 1:1000 to about 1:0.5. In a preferred embodiment, the metal compounds and the activator are mixed in a ratio ranging from approx

300:1 to about 1:1, preferably from about 150:1 to about 1:1, and for borane compounds

boranes, borates, aluminates, etc. It is preferable that the ratio range from about 1:1 to about 1:10, and for alkyl aluminum compounds (such as diethylaluminum chloride mixed with water), it is preferable that the ratio range from about 1:0.5 to about 1:10.

It is preferable to add the catalytic system, catalysts and/or activator to the reactor in one or more solutions. In one embodiment, a solution of the two catalysts is added to the alkane, such as pentane or hexane

hexane, toluene, isopentane, or something similar to a gas-phase or slurry reactor. In another embodiment the catalyst system or components thereof may be added to the reactor in a slurry, suspension or emulsion. In an embodiment, the second metal compound is contacted with an activator, such as modified methylalumoxane, in a solvent immediately before the solution is fed to a gas-phase or slurry reactor. In another embodiment, a solution of the first metallic compound is mixed with a solution of the second compound and the activator, and the resulting mixture is then added to the reactor.

In a preferred embodiment, the catalyst system consists of metal compounds (catalyst) and/or activator (cocatalyst) which are preferably added to the reactor in solution. Solutions of metallic compounds are prepared by selecting the catalyst and dissolving it in any solvent such as alkane, toluene, xylene, etc. The solvent may first be purified to remove any toxins that may affect the effectiveness of the catalyst, including any trace of water and/or oxygenated compounds. The solvent may be purified using, for example, activated alumina and a portable copper catalyst. It is preferable that the catalyst be completely dissolved in the solution to form a homogeneous solution. Both catalysts may be dissolved in the same solvent as desired. Once in solution, the catalysts may be stored for an indefinite period of time until they are used.

For the polymerization process, it is preferable to mix the catalyst with an activator before injection into the reactor. In addition, solvents and other reactants may be added to the catalyst solutions (continuously or separately), to the co-catalyst (continuously or separately), or to the activated catalyst or catalysts. There are many different configurations in which catalysts and activators can be mixed. Illustrations 1 through 9 are examples.

In the following illustrations, A refers to a catalyst or mixture of catalysts, and B refers to a different catalyst or mixture of catalysts. The mixtures in A and B can be of the same catalysts, but in different proportions. Furthermore, it is noted that additional solvents or inert gases may be added at several locations.

Illustration Method 1: A and B plus co-catalyst are mixed separately and then fed to the reactor.

Illustration method 2: Mix A and B separately. The co-catalyst is then added continuously and fed to the reactor.

Illustration 3: A and B come into contact with the co-catalyst (separately) and then A or B is added continuously before entering the reactor.

Illustration 4: A or B comes into contact with the co-catalyst (continuously) and then A or B is added continuously before entering the reactor.

Illustration 5: A and B contact the cocatalyst separately. Then A + co-catalyst and B + co-catalyst come into contact continuously before entering the reactor.

Illustration 6: A and B are in continuous contact with the cocatalyst. The A+ cocatalyst and A+ cocatalyst then come into contact continuously before entering the reactor. (This is considered a preferable form since the ratio of A to B, the ratio of co-catalyst to A, and the ratio of co-catalyst to B can be controlled separately).

Illustration 7: In this example, A or B is in contact with the cocatalyst (continuously) while an independent solution of A and B is in contact with the cocatalyst separately. Then stream 8 or B+ comes into contact with the co-catalyst continuously before entering the reactor.

Illustration 8: A is in continuous contact with B. A co-catalyst is then fed continuously into the mixture of A and B.

Illustration 9: A is activated using a separate cocatalyst. The co-catalyst A+ is then in continuous contact with B and then the co-catalyst is continuously fed into a mixture of A+ B+ co-catalyst.

Polymerization process

The catalysts and catalyst systems described above are suitable for use in any polymerization process,

Including processes in solution, gas phase, slurry or a combination thereof, preferably in phase

Ghazi or gassy.

In one embodiment, this invention directs toward polymerization or copolymerizatin reactions including the polymerization of one or more monomers containing from 2 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and preferably from 2 to 8 carbon atoms. This invention is well suited for copolymerization reactions involving the polymerization of one or more olefin monomers of ethylene, propylene, butene-l, pentene-l, and 4-methyl-pentene. -l, hexene-l, octene-l, decene-l, 3-methyl-pentene-1,

3,5,5-trimethyl-hexane-1 3,5,5-trimethyl-hexane-1 and cyclic olefins or

A combination thereof. We can ignite other monomers on vinyl monomers, diolefins such as dienes, polyenes, norbornene, and norbornadiene. It is preferable to produce a copolymer from ethylene, where the copolymer is at least one alpha-olefin containing from 3 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, preferably from 4 to 8 carbon atoms, and most preferably. From 4 to 7 carbon atoms. In an alternative embodiment, the olefins bearing the geminally disubstituted twin substituents in IPC No. 99/37109 may be polymerized or copolymerized using the invention process described herein.

In another embodiment the ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer. One of the preferred co-monomers is a combination of alpha-olefin monomers containing 4 to 10 carbon atoms, preferably 4 to 8 carbon atoms, optionally with one diene monomer.

the least. Preferred terpolymers include combinations such as ethylene/butene-1/hexene-l, ethylene/propylene butene-l, propylene/ethylene/hexene-l, ethylene/ ethylene propylene/norbornene and the like.

In a particularly preferred embodiment the process according to the invention relates to the polymerization of ethylene and at least one copolymer containing from 4 to 8 carbon atoms, preferably from 4 to 7 carbon atoms. In particular, we ignite the comonomers butene-l, 4-methyl-pentene-l, hexene-l and octene-l, the preferred comonomer of all being hexene. 1 hexene-l and/or 1-butene-l.

Typically, a continuous cycle is used in gas-phase polymerization, where in one part of the cycle of a reactor system, a cycling gas stream, also called a recycle stream or fluidizing medium, is heated in the reactor by the heat generated by the polymerization process. . This heat is removed from the recycled structure in another part of the cycle through a cooling system located outside the reactor. Typically, a gas stream containing one or more monomers in a gas-phase fluidized bed process used to produce polymers is circulated continuously through a fluidized bed in the presence of a catalyst exposed to reactive conditions. The gaseous stream is drawn from the fluidized bed and recycled to the reactor. At the same time, the polymer product is withdrawn from the reactor and a fresh monomer is added to replace the polymerized monomer (see for example US Patents Nos. 4,543,399, 4,588,790, 05,028.67, 5,367,036 , 5,352,749, 5,405,922, 50,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, all of which are fully incorporated into this statement by reference. for reference).

Reactor pressure in the gas-phase process may vary from about 10 psig (pound per square inch) (69 kilo pascals) to about

500 standard psi (3448 kPa), preferable in the range from about 100 standard psi (690 kPa) to about 400 standard psi (2759 kPa), preferable in the range from about 200 standard psi (1379 kPa) to about 400 psi (2759 kPa), best in the range from about 250 psi (1724 kPa) to about 350 psi (2414 kPa).

The reactor temperature in the gas-phase process may vary from about 30°C to about 120°C, preferably from about 60°C to about 115°C, preferably from about 75°C to 110°C, and most preferably from about 85°C to about 110°C. The change in polymerization temperature can also be used as a tool to change the properties of the final polymeric product.

The productivity of the catalyst or catalytic system is affected by the partial pressure of the parent monomer. The preferred mole percent of the main monomer, ethylene or propylene, preferably ethylene, ranges from about 25 to 90 mole percent, and the partial pressure of the monomer ranges from about 75 pounds per square inch absolute (psia) (517 kPa). ) to about 300 lb/in2 absolute (2069 kPa), which are typical conditions for a gas-phase polymerization process. In an embodiment the partial pressure of ethylene ranges from about 220 to 240 psi (1517-1653 kPa). In another embodiment, the molar ratio of hexene to ethylene in the reactor ranges from 0:1.03 to 1:0.08.

In a preferred embodiment, the reactor used in the present invention and the process of the invention produces from over 500 pounds (lbs) of polymer per hour (227 kg/hr) to about 200,000 Ib/hr (90,900 kg/hr) or More than polymer, preferably over 1,000 lb/h (455 kg/h), best over 10,000 lb/h (4,540 kg/h), best ever over 25,000 lb/h (11,300 kg/h) , better yet, over 35,000 lbs/hour

(15,900 kg/h), preferably more than 50,000 lb/h (22,700 kg/h), and most preferably more than 65,000 lb/h (29,000 kg/h) to more than 100,000 lb/h (45,500 kg/h). /hour).

Other gas-phase processes within the scope of the invention include processes described in U.S. Patent Nos. 5,627,242, 5,665,818, and 677,375.5 and European Patent Publications Nos. 794200-0-A, 202-802-0-A. and 421 34 6-B, all of which are mentioned in this statement for reference.

The slurry-phase polymerization process typically uses pressures in the range from about 1 to about 50 atmospheres and even higher pressures and temperatures in the range from 0°C to about 120°C. In a slurry-phase polymerization process, a suspension of solid particulate polymer is formed in a dilute liquid polymerization medium to which ethylene, co-monomers, and often hydrogen are added along with the catalyst. The suspension containing the diluent is removed intermittently or continuously from the reactor where the volatile components are separated from the polymer and recycled, optionally after distillation into the reactor. The diluent includes the liquid used in the polymerization medium, usually an alkane with 3 to 7 carbon atoms, preferably a branched alkane. The medium used should be liquid under polymerization conditions and relatively inert. When a propane medium is used, the process should be operated at a temperature and pressure above the critical temperature and pressure of the reaction buffer. It is preferable to use a medium of hexane or isobutane

isobutane.

In an embodiment, a preferred polymerization technique according to the invention is referred to as particle form polymerization, or a froth-phase process where the temperature is maintained below the temperature at which the polymer turns into solution. A technique of this nature is well known in the art, and is described for example in US Patent No. 3,248,179 which is cited herein by reference. The preferred temperature range in the polymerization process

In particulate form from about 185°F (85°C) to about 230°F (110°C). Two preferred polymerization methods for a slurry-phase process include those that use an Ioop reactor and those that use multiple stirred reactors arranged in series, parallel, or a combination thereof. Examples of slurry-phase processes include, but are not limited to, continuous-loop or stirred-tank processes. Other examples of slurry-phase processes are also described in US Patent No. 4,613,484, which is cited herein for reference.

In another embodiment, the process is conducted in the slurry phase continuously in a toroidal reactor.

The catalyst in the form of a solution, suspension, emulsion or slurry in isobutane or as a dry free flowing powder is uniformly injected into the reactor loop, which itself fills a circulating slurry of growing polymer particles in a diluent of A monomer and a comonomer containing isobutane. Hydrogen is optionally added as a molecular weight control. The reactor is maintained at a pressure ranging from about 525 standard psi to 625 standard psi (3620 kPa to 4309 kPa) and at a temperature ranging from about 140 F to about 220 F (about 60 C to about 104 C) based on The desired polymer density. The heat of reaction is removed through the loop wall, as most of the reactor is in the form of a double-jacketed pipe. The slurry is allowed to exit the reactor at regular intervals or continuously into a heated low-pressure flash vessel, rotary dryer, and nitrogen purge column sequentially to remove the isobutane diluent and all unreacted monomers and comonomers. The resulting hydrocarbon fleece powder is then prepared in the form of compounds for use in various applications.

In one embodiment, the reactor used in the slurry-phase process according to the invention and the process of the invention are capable of producing in excess of 2,000 pounds of polymer per hour (907 kg/hour), preferably in excess of 5,000 pounds/hour (2,268 kg/hour), and most preferably some Over 10,000 lbs/hr (4,540 kg/hr). In another embodiment, the slurry phase reactor used in the process of the invention produces in excess of 15,000 lb/h (6,804 kg/h), preferably in excess of 25,000 lb/h (11,340 kg/h) to about 100,000 lb/h (45,500 kg/hour). In another embodiment, in the slurry-phase process of the invention the total reactor pressure ranges from 400 standard psi (2758 kPa) to 800 standard psi (5516 kPa), preferably from 450 standard psi (31.03 kPa) to About 700 psi standard (4827 kPa), best from about 500 psi standard (3448 kPa) to about 650 psi standard (4482 kPa), most preferable from about 525 psi standard (3620 kPa). ) to 625 standard psi (4309 kPa). In another embodiment, in the slurry-phase process of the invention the ethylene concentration in the liquid reactor medium ranges from about 1 to 10% by weight, preferably from about 2% to about 7% by weight, preferably from about 2.5 to about 6% by weight, and most preferably from about 2% to about 7% by weight. About 3 to about 6% by weight.

According to the invention, the preferred species is the species, and it is preferable to have a sluggish or gaseous phase.

which operate in the absence or which are essentially devoid of any scavengers, such as triethylaluminum, trimethylaluminum; tri-isobutylaluminum and tri-n-hexylaluminum

Diethyl aluminum chloride, dibutyl zinc, and the like. This preferred process is described in the International Patent Bulletin in accordance with Patent Cooperation Treaty No. 96/08520 and US Patent No. 5,712,352, which are cited herein by reference.

In another preferred embodiment, one or all of the catalysts are mixed with not more than 10% by weight of metal stearate (preferably aluminum stearate, preferably aluminum distearate) based on the weight of the catalyst system (or components thereof) and any carrier and stearate stearate. In an alternative embodiment, a solution of metal stearate is fed to the reactor. In another embodiment, the metal stearate is mixed with the catalyst and the product is fed to the reactor in a separate form. These agents may be mixed with the catalyst or may be fed to the reactor in solution or slurry with or without the catalyst system or its components.

In another preferred embodiment, the portable catalysts are tumbled and doped with 1% by weight of aluminum distearate or 2% by weight of an antistatic, such as a methoxylated amine, such as Kemamine AS-990. AS named Witco's from ICI Specialties in Bloomington, Delaware. In another embodiment a portable catalytic system of the component is blended with 2 to 3% by weight of metal stearate, based on the weight of the catalytic system (or components thereof) and any carrier and vehicles.

stearate.

More information on the use of aluminum stearate additives can be obtained in US Patent Application No. 09/113 261 filed on July 10, 1998, and US Patent No. 6,031 filed on February 29, 2000, which are mentioned in this article. Statement for reference.

In a preferred embodiment a slurry of stearate in mineral oil is fed to the reactor separately from the metal compounds and/or activators.

The catalyst and/or activator may be placed on a carrier, deposited on, contacted with, incorporated with, adsorbed or absorbed. The carrier can usually be any solid porous carrier, including microporous carriers. Typical carrier materials include talc; Inorganic oxides

inorganic oxides such as silica, magnesium chloride, alumina, and silicaalumina and polymeric supports such as polyethylene, polypropylene, polystyrene, and cross-linked polystyrene; And so on. It is preferable to use the adverb in its finely divided form. It is preferable to remove the dehydrated water from the holder partially or completely before use. Water may be removed physically by calcination, or chemically by converting all or part of the active hydroxyls. For more information on how to carry catalysts, see US Patent No. 4,808,561, which describes how to carry a metallocene catalyst system. The techniques used in this patent are usually applicable to this invention.

In another embodiment, a selective poison is added to the polymerization process which selectively deactivates one of the catalysts in a controlled manner and thus controls the efficient cleavage of the resulting polymer. Preferred selective poisons include carbon dioxide, carbon monoxide, olefins and various endogenous dienes, oxygen, and Lewis bases such as ethers, esters, and various amines.

In a preferred embodiment the resulting polymer in this statement has an I21 value (as measured in accordance with ASTM 1238 American Society for Testing Materials, Section E, at a temperature of 190°C) of 20 g/10 minutes or less, preferably 15 g 10 minutes or less, preferably 12 or less, preferably between 5 and 10 g/10 minutes, preferably between 6 and 8 g/10 minutes and MIR melt flow index of I2/I21 (as measured by ASTM 1238, Clause E , At a temperature of 190°C) it is 80 or more, preferably 90 or more, preferably 100 or more, preferably 125 or more.

In another embodiment the polymer has a value of I21 (as measured by ASTM 1238, Clause E,

At 0 9 1 m) 20 g/10 minutes or less, preferably 15 g/10 minutes or less, preferably 12 g/10 minutes or less, best between 5 and 10 g/10 minutes, best between 6 and 8 g/10 Minutes and night MIR magma flow for I21/I2 (as measured by ASTM 1238, Section E and Section F, at 0.91°C) is 0.8 or greater, preferably 0.9 or greater, preferably

100 or more, preferably 120 or more and having one or more of the following properties: (a) Mn/Mw between 15 and 80, preferably between 20 and 60, preferably between 20 and 40;

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

(d) Density (as measured in accordance with ASTM 2839) ranging from 0.94 to 0.970 g/cm3, preferably from 0.945 to 0.965 g/cm3, preferably from 0.948 to 0.955 g/cm3; (e) A residual metal content of 200 ppm of the transition metal or less, preferably 1.8 ppm of the transition metal or less, preferably 1.06 ppm of the transition metal or less, preferably 1.5 parts. per million transition metal or less, preferably

2.0 ppm or less of a Group 4 metal, preferably 1.8 ppm or less of a Group 4 metal, preferably 1.6 ppm or less of a Group 4 metal, preferably 1, 5 ppm or less of a Group 4 metal, preferably

200 (as It was measured by Inductively Coupled Plasma Optical Emission Spectroscopy, which is performed on commercially available standards, where the sample is heated to completely decompose all the organics, and there is a solvent containing acid. nitric acid, and another acid if any carrier is present, to dissolve any carrier (such as hydrofluoric acid to dissolve silica supports);

(f) 35% or more by weight of a component having a high molecular weight average, as measured by sizeexclusion chromatography, preferably 40% or more. And in embodiment

Particularly preferable is the high molecular weight fraction with a concentration between 35 and 70% by weight, preferably between 40 and 60% by weight.

The molecular weight (Mw and Mn) is measured as described below in the examples section.

In another embodiment the polymeric product has a residual metal content of 2.0 ppm transition metal or less, preferably 1.8 ppm transition metal or less, preferably 1.6 ppm transition metal or less, preferably 1 5 ppm of a transition metal or less, preferably 2.0 ppm or less of a Group 4 metal, preferably 8, 1 ppm or less of a Group 4 metal, preferably 1.6 ppm or less of a Group 4 metal, preferably 1.5 ppm or less of a Group 4 metal, preferably 2.0 ppm per million or less zirconium, preferably 1.8 ppm or less zirconium, preferably 1.6 ppm or less zirconium, preferably 1.5 ppm or less zirconium (as measured by Inductively coupled plasma photoemission spectroscopy performed on standard materials is available Commercially, the sample is heated to completely dissolve all organic compounds and there is a solvent containing nitric acid and another acid, if any carrier is present, to dissolve any carrier (such as hydrofluoric acid to dissolve silica carriers

silica supports).

In another embodiment the polymeric product has a residual nitrogen content of 2.0 ppm or less, preferably 1.8 ppm nitrogen or less, preferably 1.6 ppm nitrogen or less, preferably 5, 1 ppm nitrogen or less (as measured by inductively coupled plasma optical emission spectroscopy performed on commercially available standards, where the sample is heated to completely dissolve all organic matter and a solvent containing nitric acid and another acid is present

If any carrier is present, to dissolve any carrier (eg hydrofluoric acid to dissolve silica supports).

In another embodiment, the resulting polymer of this invention has a composition distribution breadth index (CDBI) of 70 or more, preferably 75 or more, and preferably 80 or more. The composition distribution breadth coefficient is a means to measure the distribution of the covalent monomer among the polymer chains in a specific sample. CDBI is measured according to the procedure described in International Patent Application No. 30930/93, issued on February 8, 1993, provided that the parts have a molecular weight of less than 10,000 and Mn is neglected when calculating.

In a preferred embodiment, the extracted polyolefin has a magma index (as measured in accordance with ASTM D-1238, Section E, at a temperature of 190°C) of 3000 g/10 min or less. In a preferred embodiment, the polyolefin is a homopolymer or copolymer of ethylene. In a preferred embodiment for certain applications, such as films, molded article, and the like, the skill index is preferred to be 100 g/10 minutes or less. For some membranes and the material generated, it is preferable to reach the index of magma

10 g/10 minutes or less.

In a preferred embodiment, the catalytic system described above is used to prepare polyethylene having a density of between 0.94 and 0.970 g/cm3 (as measured by ASTM 2839) and a magma index of 0.5 g/10 minutes or less (as measured by ASTM 1238). -ASTM D item E, at a temperature of 190°C).

It is preferable to produce polyolefin with a magma index ranging from 0.01 to

10 decigram/minute dg/min•

Polyolefins, especially polyethylenes with densities ranging from 0.89 to 0.97 g/cm3, can be produced using the present invention. Polyethylenes, in particular, can be produced with densities ranging from 0.910 to 0.965, preferably from

0.915 to 0.960, preferably 0.920 to 0.955 and in some embodiments, a density ranging from 0.915 to 0.940 g/cm3 is preferred, and in other embodiments a density ranging from 0.930 to 0.970 g/cm3 is preferred.

Polyolefins can then be formed into films, molded materials (including pipes), sheets, coatings for wires and cables, and the like. Films can be formed using any conventional method known to the technology including extrusion, co-extrusion, lamination, blowing and casting. The membrane can be obtained through a flat film or tubular process, which may be followed by orientation in a uniaxial direction or in two mutually perpendicular directions in the plane of the membrane to a similar or different degree. The guidance may be the same degree in both directions or it may be to a different degree. Particularly preferred methods for forming polymers into films include extrusion or co-extrusion on a film line by blowing or casting.

Formed films may also contain additives such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistatics, and auxiliary agents. For polymer processing aids, neutralizers, lubricants, surfactants, dyes, dyes, nucleating agents. Preferred additives include silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, carbonate.

Calcium carbonate, metal stearates, calcium stearate, zinc stearate, talc, and BaSO4, diatomaceous earth, wax, carbon black, flame retarding additives, low molecular weight resins , hydrocarbon resins

hydrocarbon resins' glass beads and the like. Additives may be present in the typical effective amounts well known in technology, such as 1.001% by weight to 10% by weight.

Examples

Mw and Mn were measured by gel permeation chromatography (GPC) using a waters instrument for GPC at a temperature of 150°C equipped with differential refraction index detectors. GPC columns were calibrated by pouring a series of polyethylene molecular weight standards and molecular weights were calculated using Mark Houwink coefficients for the polymer of the invention.

Density was measured according to the ASTMD 1505 procedure.

The magma index (mi) for I2 and I21 was measured according to procedure 1238-asTM D, clauses e and f, at a temperature of 1.90°C.

The skill index ratio (mir) represents the ratio of I21 over I2 as determined according to the 1238-asTM D procedure.

The weight percentage of the copolymer was measured using proton nuclear magnetic resonance (NMR).

Mn/Mw = mwd

I21 was measured according to procedure 1238-ASTMD, section E, at a temperature of 190°C.

PPH&amp;&amp; represents pounds per hour. &amp;mPPH&amp; represents millipounds per hour.

&amp;PPmw&amp; represents parts per million by weight

In NMR spectra, the symbols indicate the following:

Delta (c): difference, q: single spectrum, g: double spectrum, w: triple spectrum, t: quadruple spectrum, e: multiple spectrum, c: joule unit, Hz: Hz.

Catalyst A is tribenzyl[1-2-pyridyl)-N-1-methylethyl]

[1-N-6,2-Diisopropylphenylamido]Zirconium [1-(2-Pyridyl)N-1-Methylethyl][1-N-

2,6Diisopropylphenyl Amido]Zirconium Tribenzyl and prepared as follows: Preparation of [1-(2-Pyridyl)-N-1-methylethyl][1-N-6,2-diisopropylphenyl]amine-[1(2-Pyridyl)Nl

Methylethyl][1-N- 2,6- Diisopropylphenyl]Amine

<img file="SA735B1_D0008.tif" />

In a dry box Charged 6.34 g (22.45 mmol) of acetylpyridine (2,6-diisopropylphenylimine) to a round bottom flask Capacity: 250 ml, dial with stir bar and septa barriers. The vial was sealed, removed from the dry box and placed in a nitrogen purge. Add 50 ml of dry toluene and stir to dissolve the ligand. The vessel was suddenly chilled to zero degrees Celsius in a wet ice bath. Trimethyl aluminum (provided by Aldrich, at a concentration of 2.0 M in toluene) was added drop by drop over 10 minutes. The reaction temperature was not allowed to exceed 10°C. When the addition of trimethyl aluminum was complete, the mixture was left to warm slowly to room temperature, then it was placed in an oil bath and heated to a temperature of 40°C for 25 minutes. Remove the vessel from the oil bath and place it in an ice bath. A dropping funnel containing 100 ml of 5% KOH was attached to the flask. The caustic material was charged to the reaction point by point over a time period of one hour. The mixture was transferred to a separatory funnel, and the aqueous layer was removed. The solvent layer was washed with 100 ml of water, then 0.1 ml of water

Brine water. The red-brown liquid product was dried over Na2S04, vacuum stripped and placed at high vacuum overnight.

high vacuum.

Transfer 80 ml of the reddish-brown liquid to a 200 ml Schlenk flask equipped with a stir bar. A distillation head containing a condenser using dry ice was attached to the flask. The mixture was distilled under vacuum, resulting in the production of approximately 70 g of a dark yellow viscous liquid product. Preparation of tribenzyl[1-(2pyridyl)-N-1-methylethyl][1-N-6,2-diisopropylphenylamido]

Zirconium 1-(2- Pyridyl)Nl- Methylethyl][1-N- 2,6-Diisopropylphenyl Amido] Zirconium Tribenzyl]

<img file="SA735B1_D0009.tif" />

In a darkened room and darkened dry box, charge 1.45 g (5.0 mmol) of the ligand prepared in Example 1 into a 100 mL Schenk tube fitted with a stir bar. The ligand was dissolved in 5 ml of toluene. To a second vessel equipped with a stirring rod, charge 2.5 g (5.5 mmol) of tetrabenzyl zirconium and 10 ml of toluene.

The ligand solution was transferred to a tetrabenzyl zirconium solution. Cover the container with foil and leave it to stir at room temperature in the dry box. After 6 hours at room temperature, 80 ml of dry hexane was added to the reaction solution and left to stir overnight. The reaction mixture was filtered through a medium porosity frit so that about 2 g of pale yellow solids were collected.

Catalyst B is tetrahydroindenyl zirconium tris pivalate, which is a metallocene compound that contains a bulky ligand that can be prepared by performing the following general reactions:

Zr (NEt2)4 + IndH→IndZr (NEt2)3 + Et2NH (1)

IndZr (NEt2)3 + 3(CH3)3 CCO2H→ IndZr[O2CC(CH2)]3 + Et2NH (2)

Where Ind represents tetrahydroindenyl Et and tetrallydroindenyl represents ethyl. Catalyst C is produced as follows:

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

Add to a 2-liter one-armed Schlenk flask equipped with a magnetic stir bar 23,450 g (0.227 mol) of diethylenetriamine and 90.51 g mol) of 2-bromomesitylene, 1,041 g. (1.14 mmol) of tris(dibenzylideneacetone)dipalladium, 2,123 (3.41 mmol) of 2,2'-(diphenylphospino)-1,1'-racemic dinaphthyl (BINAP RACEMI)

(racemic-2,2'-bis( diphenylphosphino )1,1' -binaphthyl (racemic BINAP), 65.35 g (0.682 mol) of sodium tertbutoxide, and 800 ml of toluene in a dry nitrogen-free atmosphere Oxygen free nitrogen. The reaction mixture was stirred and heated to a temperature of 100°C. After 18 hours, the reaction was completed, as determined by proton Ni spectroscopy, and all remaining solvent was removed in vacuum and the concentrate was evaporated in 1 liter. L) of diethyl ether. The ether was washed three times with water using 250 ml each time, then using (180 g in 500 ml) of saturated aqueous NaCl and dried over 30 g of magnesium sulfate. The removal of ether in vacuum resulted in 71.1 g of red oil, which was dried at a temperature of 70°C for 12 hours in vacuum (average

Production = 92%0 1H R N M (C6D6) Delta 6.83 (F, 4), 3.39 (F, 2), 2.86 (W, 4), 2.49 (W, 4) , 2.27(F, 12), 2.21(F, 6), 0.68(F, 1).

Catalyst preparation c

Prepare a solution of Catalyst C at a concentration of 1.5% by weight in toluene. Note: All procedures were carried out in a box with gloves.

1- Weigh 10 grams of purified toluene in a 1-liter Erlenmeyer flask equipped with a Teflon-coated stirring bar.

2- Add 7.28 grams of tetrabenzyl zirconium.

3- Place the solution on the agitator and stir for 5 minutes. All solids in the solution germinate.

4- Add 5.42 g of ligand I.

5- Add another amount of toluene, amounting to 551 grams, and leave the mixture to stir for 15 minutes. No solids remained in the solution.

6- Pour the catalyst solution into a clean and purified Whitey cylinder with a capacity of 1 liter, label it, remove it from the glove box and place it in the holding area for operation.

Alternative preparation method for {2(2,4,6-Me3C6H2) NCH2CH2]2NH}Zr (CH2Ph)]}

Charge a 500 ml ball-bottom flask with a magnetic stir bar with 41.729 g (91.56 mmol) of tetrabenzyl zirconium (provided by Boulder Scientific) and 300 ml of toluene in a dry, free nitrogen atmosphere. Of oxygen oxygen free nitrogen. Add 32.773 g (96.52 mmol) of the solid ligand I mentioned above and stir for one minute (precipitation of the desired compound). The volume of the slurry was reduced to 100 ml and 300 ml of pentane was added while stirring. 44.811 grams of the yellow-orange solid product was collected by filtration and dried in vacuum (production rate = 80%). 1H R N M (C6D6) delta

7.22-6.81(A, 12), 5.90 (G, 2), 3.38 (D, 2) 1 3.1 (A, 2), 3.01 (A, 1), 2, 49(F, 4), 2.43(F, 6), 2.41(F, 6), 2.18(F, 6), 1.89(F, 2), 0.96(F, 2) ).

Catalyst D is indenyl zirconium tris pivalate, which is a metallocene compound that contains a bulky ligand prepared by performing the following general reactions:

(1) Zr(NEt2)4 + IndH→IndZr(NEt2)3 + Et2NH

(2) IndZr(NEt2)3 + 3(CH3)3CCO2H→IndZr[O2CC(CCH3)]3 + Et2NH

Where Ind represents indenyl, Et and indenyl represents ethyl.

Example 1

Run both catalysts at the same time

A copolymer of ethylene and hexene was produced in a pilot plant scale gas-phase reactor with a diameter of 14 inches (35.6 cm) operated at a temperature of 85°C and a total reactor pressure of 350 psi (2, 4 MPa) and contains a water-cooled heat exchanger. The reactor was equipped with a plenum containing approximately 1,600 pounds per hour of recycle gas flow. (A filler is a device used to create a particle, lean zone in a fluidized bed gas-phase reactor, see US Patent No. 5,693,727.) A tapered catalytic nozzle with a hole diameter of 0.041 inches (0.1 cm) is placed in the plenum gas flow. Before starting to feed the catalyst, the ethylene pressure was about 220 psi (1.5 MPa), the 1-hexene concentration was about 0.6 mol%, and the hydrogen concentration was about 0.25 mol%. Nitrogen is supplied to the reactor as make-up gas at about 5 to 8 lb/hour. The catalyst solution was catalyst A and catalyst B in gram molar ratio

It was 1:1 in toluene solution. The catalyst was fed at a rate of 13 cubic centimeters (cc's) per hour, which was sufficient to obtain the desired production rate of 17 lbs/hour. The catalyst and activator (consisting of modified methylalumoxane, MMAO-3A, 1% aluminum) were mixed. Commercially available weight from Akzo Chemicals, Inc. With the trade name Modified Methylalumoxane Type 3A, which is protected in US Patent No. 5,041,584) in the feed line before passing through the injection nozzle to the fluidized bed. The ratio of MMAO to catalyst was adjusted so that the molecular gram ratio of 1:300 Zr:Al. Also feed 5.0 lb/h (2.3 kg/h) of nitrogen and 0.20 lb/h (0.1 kg/h) of 1-hexane to the injection nozzle. He obtained a bimodal polymer whose nominal value (I21) was 0.43 dg/min and whose density reached 0.942 g/cm3. The average resin particle size was 0.023 inches (0.06 cm). The remaining zirconium concentration was 2.20 ppm by weight and was measured by X-ray fluorescence.

Example 2

Run using a high molecular weight catalyst first

A copolymer of ethylene and hexene was produced in a 14-inch (35.6 cm) pilot-scale gas-phase reactor operated at 85°C and an overall reactor pressure of 350 psi (2.4 MPa). It has a water-cooled heat exchanger. The reactor was equipped with a filler containing approximately 1,600 pounds per hour of recycled gas flow. (A filler is a device used to create a particle-poor zone in a fluidized bed gas-phase reactor, see US Patent No. 5,693,727.) A tapered catalytic injection nozzle with a 0.055 inch (0.14 cm) diameter gap is placed in the filling gas flow. Before starting to feed the catalyst, the ethylene pressure reached about 220 psi (1.5 MPa), and the concentration was

1-L-hexane is about .3 mol%, and the hydrogen concentration was about 0.12 mol%.

The catalyst C was mixed in a solution of 0.5% by weight in toluene and fed into the reactor at a rate of 12 cm/hour. A co-catalyst of MMAO-3A (1% by weight aluminum) was mixed with the catalyst in the feed line before entering the reactor in a molecular ratio. A gram of 1:400 of Zr:Al. The production rate was approximately 2.4 lb/hour (10.9 kg/hour). In addition, it is also enriched with 5.0 lb/h (2.3 kg/h) of nitrogen, 0.1 lb/h (0.05 kg/h) of 1-hexane, and 0.2 lb/h (0 09 kg/hour) of isopentane to the injection nozzle. The polymer has a flow index of 0.31 dg/min and a density of 0.935 g/cm3. After achieving this, the catalyst feed rate was reduced to 6 cm3/hour of catalyst C and 0.125% by weight of indenyl zirconium tris pivalate (catalyst D) in the hexane feed solution was added to the injection line at a rate of 13 cm3/hour. The overall order of addition was hexene, then MMAO was added mixed with a solution consisting of catalyst D/catalyst C, then isopentane and nitrogen. The Zr/Al ratio for the complete system was about 500. Within six hours of adding catalyst D, the bimodal polymer had a nominal I21 value of 12.9 dg/min, a multi flow rate (MFR) of 130, and a density of 0.953 g/cm3. The average resin particle size was 0.0479 in. (0.12 cm). The amount of zirconium remaining was 0.7 ppm by weight and was measured by X-ray fluorescence.

Example 3

Operation using a low molecular weight catalyst

A high density high molecular weight (HMWHD) layer was produced from a bimodal catalytic system. The catalyst produced component D

Low molecular weight component (LMWC) and produced high molecular weight component (HMWC).

Before starting the catalyst checking, the reactor conditions were as follows. The layer temperature was 85°C, the total pressure was 350 psi (2.4 MPa), the partial pressure of C2 was 220 psi (15.2 MPa), the C2/C6 ratio was 0.005, and the concentration of H2 1200 ppm. The carrier flow of N2, tied to the catalytic flow line approximately 5 ft (1.52 m) long from the injection port, begins at a rate of 2.0 lb/in2 (0.91 kg/h). ). Shroud nitrogen, which helps form a particle-free zone at the catalytic injection point of the reactor, begins flowing at a rate of 2.5 lb/in2 (1.13 kg/h).

Catalyst D was fed at a concentration of 0.125% by weight in hexane solvent to the reactor first at a flow rate of 20 cm3/hour. A small amount of hexene kiss added to the system came into contact with the catalyst immediately after the syringe pump and helped carry the catalyst downward. The volumetric ratio of the small amount of hexene to the catalyst D was set at 2.70, and the MMAO (consisting of Al with a concentration of 3.55% by weight in hexane) is contacted with the current consisting of the catalyst D/small amount of hexene through a coil of size 100. cm3 MIO flux such that the molar ratio of Zr:Al reached 700.

Before adding HMWC, the correct product of LMWC was formed. The desired magma index was 550 dg/min, which was obtained by adjusting the hydrogen concentration. The hydrogen concentration at work was 1200 parts per million, which resulted in a magma index of approximately 350 dg/min. Thus, the hydrogen concentration was set at 1350 ppm to obtain a product with a magma index of 0.55 dg/min.

Once the desired product was obtained from the LMWC, the catalyst C was fed at a rate of 6.8 cm3/h. Thus, he obtained a molecular percentage of 1.5 from the catalyst C: catalyst

Dr.. The catalyst stream C is mixed with the catalyst stream D after the contact of the catalyst D and the MMAO with the coil. This stream goes to the reactor through a 0.055 inch (0.14 cm) diameter injection nozzle. The I21 value of the formed product was 8.24 dg/min, the product density was 0.950 g/cm3, the average particle size (AFS) was 0.0224, and the remaining zirconium concentration was 0.80 ppm by weight. It was measured by fluorescence X ray.

All references cited in this statement are for reference, including any prior documentation and/or testing procedures. As is evident from the foregoing general description and specific embodiments, although variations of the invention have been stated and described, various modifications may be made without departing from the scope and principle of the invention. Accordingly, the invention is not limited to these forms.