SA00210262B1 - Catalytic synthesis, method for polymerization, and the resulting polymer - Google Patents

Abstract

Abstract : The present invention relates to catalyst compositions and methods, useful in polymerization processes, using at least two metal compounds. One of the two metalloids is a Group 15 containing metal compound and preferably the other is a bulky ligand metallocene-type catalyst. The invention also relates to a new polyolefin, usually polyethylene, and in particular a multimodal polymer and more specifically, a bimodal polymer, and its use in applications

Description

Y

catalytic installation method for polymerization and the resulting polymer Full description Background of the invention It includes a catalyst composition The present invention relates to a catalyst composition

Oily at least useful in the processes of polymerization of metal compounds two metal compounds to produce polyolefins 0017016505. It is preferable that one of the olefin polymerization processes 11 at least two metal compounds is a metal compound containing an element of the group AY ) and it is preferable that the metal compound be Group 15 containing metal compound bulky ligand metallocene-type. Polyolefin The present invention also relates to a polyolefin catalyst and more specifically a multimodal polymer; In particular, a multi-modal polyethylene polymer and its use in various final applications such as the manufacture of cbimodal polymer, pipe and pipe molding, molding ¢film, and the weight of polyethylenes that have a density. Polyethylene 01 films that require a high dela hardness are of interest in molecular weight applications.

Glad) is high. It also has good throughput and high productivity; toughness Alia is high; such stiffness is of importance in pipe making applications that require rigidity; The durability of Fas al al Bithy resins and their clong-term durability and long-term endurance in particular. Models (ie, those containing a single transition metal fluorenyl or an indenyl <cyclopentadienyl with a cyclopentadienyl group having at least latiHl strength properties) to produce resins having desirable product properties. And while for this

AAY

Excellent; Especially the cdart impact properties Jie terminated polyethylene 4a polyethylenes ¥ 3 with metallocene other difficult-to-manufacture metallocene; For example; using old extrusion equipment. One method used to improve the process of making metallocene-catalyzed polyethylenes from this type 0 is to mix it with another polyethylene. While a mixture of two polymers may be more processable, this is expensive and adds a cumbersome mixing step to the manufacturing/fabrication process. High molecular weight conferring desirable mechanical properties and stable bubble formation for polymers. From polyethylene, other than ye, it also stands Sila without extrusion processing due to the increased back pressure in the extruders and promotes the appearance of melt fracture defects in the bubble The cinflating bubble may greatly enhance the degree of orientation in the finished film, and to address this; A minor component can be formed from a lower molecular weight polymer vo to lower the back pressure in the slotting tool and to inhibit fusion fracture. Various industrial processes are operated on this principle using multiple reactor technology to produce a processable high density polyethylene (HDPE) product with uniform eu (MWD) molecular weight distribution. HIZEX (trademark) is HIZEX™ +. It is a Je (HDPE) high density polyethylene product obtained from Mitsui Chemicals and is considered a worldwide standard and produces HIZEX (trademark) HIZEX™ In an expensive process using two or more reactors0 and in a “multiple reactor process” each reactor produces one component of the final product AAY

¢ Others in the technique have attempted to produce two polymers simultaneously in the same reactor using two different catalysts. The international patent application pursuant to PCT No. 078494/99 describes the use of a typical metallocene catalyst and a conventional Ziegler-Natta catalyst in the same reactor to produce HDPE of 0 molecular weight distribution. Bimodal. However, the use of two different types of catalysts” leads to the production of a polymer with properties that cannot be expected compared to the properties of those polymers that may result from the use of the two catalysts separately. The unpredictability of these properties is due, for example, to competition or any other influence between the catalyst or catalyst systems used. However, these polymers are not preferred in terms of aia Wl and strength properties 1 and therefore; It is desirable to combine catalysts capable of producing ALE polyethylene polymers for processing, preferably in a single reactor with combined desirable processing, mechanical and optical properties. GENERAL DESCRIPTION OF THE INVENTION The present invention provides a catalytic composition; polymerization process using catalytic synthesis; © Polymer and products made from polymer. z and in one embodiment; The invention is directed toward a two-metallic catalytic composition on (JY) where at least one of the two metals is a metallocene containing a group V0 element and where the other metalloene is a metallocene-type compound containing a bulky ligand; A conventional transition metal catalyst, or combinations thereof. In one embodiment; The invention is directed toward a catalytic composition comprising two metalloids on (JY) where at least one of the two metalloids is a metallocaine containing a group 00 element and the other metallocaine is a metallocene-type compound containing a bulky ligand; or a conventional transition metal catalyst, or combinations thereof. ANY

In one embodiment; The invention is directed towards a metal composition containing at least two metal compounds; Where one of the two metal compounds is a metal compound containing one of the groups element? To a VE bound with a bidentate tridentate containing an element from group V0 and preferably from groups ? to ; and better than 0 groups; to 1 and more preferably also a metal compound containing a group 4 metal; and where the other metallic compound is a metallocene-type compound containing a large ligand; or a conventional transition metal catalyst; or combinations thereof, the other metal compound in this embodiment is preferably a metallocene-type compound containing a :0 ligand and in another embodiment; The invention is directed toward a catalytic composition comprising two metal compounds on (JAY) wherein one of the two metal compounds is a metal atom of groups * to VE bonded to at least one removable leaving group dc sane also bonded to at least two atoms of group 1015 where at least one of them is also linked to an atom of group 05 or 11 through the os AT group and where the second metal compound is lisa from the first metal oe compound; It is a metallocene-type catalyst containing an Ada ligand; a transition metal catalyst of the conventional type; or combinations thereof. In one embodiment; The invention is directed toward processes for the polymerization of olefin(s) using the catalytic compositions described above; especially in a single polymerization reactor ' and in the AT embodiment as well; The invention is directed towards polymers prepared using the catalytic compositions mentioned above and preferably density Je polyethylene having a new bimodal molecular weight distribution. AAY

+ Brief explanation of the drawings and in the following illustrations; a refers to a catalyst or a mixture of catalysts; and b denotes a different catalyst or a mixture of different catalysts. The mixtures of catalysts in a and b may be isomeric; But in different proportions. In addition; It is noted that additional solvents or inert gases ert gases 0 can be added in several locations. Illustration 1: A and B plus the activator are mixed separately and then fed to the reactor. Illustration?: Mix A and B separately. Then the activator is added continuously and then fed to the reactor. Illustration “: A or B come into contact with the activator (separately); Hence AOP6 is added inside the pipeline before entering the reactor. Illustration: A or B comes into contact with the activator (continuously); Then A or B is added inside the pipeline before entering the reactor. Fig. 10 A and B come into contact with the activator separately. B and activator B then come into contact with the activator inside the pipeline before entering the reactor. Figure 1: A and B are in contact with the activator Jah of the pipeline. Then A with the activator and B with the activator, Jabs, come into contact with the pipeline before entering the reactor. (This is the preferred combination Tks because the A-to-B ratio, activator-to-A ratio, and activator-to-B ratio can be controlled separately). Illustration 7: In this example; A or B contacts the activator (continuously) while 9 separate solutions of A or B contact the activator separately. Then both streams A or B come into contact with the activator inside the pipeline before entering the reactor. Figure +: A is in contact with B in a continuous manner. Then the activator is fed into the pipeline leading to the mixture of A and B. Figure 4: Activates A using the activator separately. Then a and the activator come into contact with b ve in contact. The activator is then fed into the pipeline leading to the mixture of activator A and activator B. AAY

Detailed Description The present invention relates to the use of a mixed catalyst composition where one of the two catalysts is a metal compound containing an element of group V0 and the applicants discover that using these compounds in combination with a cal catalyst is preferable to a M0 compound. Of the metallocene type, it has a large ligand; A new product is produced from le polyethylene HDPE with a bimodal molecular weight distribution. Surprisingly, the mixed catalytic composition Gag of the present invention (Say) can be used in a single reactor system. A metallic compound containing an element of group Vo The mixed catalytic composition Gay of the present invention comprises a From group V0 and the compound that contains an element from the group Loses Ve contains a metal atom from the groups “to VE” and it is preferable from the groups “NIT” and the best from the groups; to 1; and it is also more preferable to choose the metal atom from The group is bonded to at least one easily removeable group and also to at least two atoms of group V0 such that at least one of them loads to an atom of group Vo or VV through another group. AIX at least one of the atoms of group 10 is bonded to an atom of group 11 or 11 via another group that may be a hydrocarbon group n to a hydrocarbon group of to © (has from 1 to 10 carbon 0 atoms (carbon or dc gana) containing a heteroatom cheteroatom silicon 811::00; germanium Y. tin lead clead or phosphorus Cua phosphorus An atom of group 15 or 11 may also not bond with any group or may bond with a hydrogen chydrogen a group containing an atom of group 40 a halogen or de gana containing a hetero atom; And where both atoms of group V0 are also attached to a cyclic group and may bond to a hydrogen halogen hetero-atom or a hydrocarbyl group ve or a group that optionally contains a hetero-atom. ANY

A

which contains an element of the set os tall and in a preferred embodiment; The compound of the present invention may be represented by the following formulas: ag 05 "4 rR? Rr [ formula oY wl ex...

NN, /

RZ

IN.

ROR

or 4 II Formula 1 RY

Retrieved by CNN for MS Mag.” r ws where main group or a metal from the main group 11 does not represent a transition metal from the groups? to 00 or ; and the best metal from group 4; © of groups TH and preferably VE or 0 <hafnium or hafnium titanium zirconium and most preferably zirconium <anionic: separately easy-to-remove group; An easily removed anionic group X is preferred, and each heterocarbyl atom represents a hydrocarbyl group, chydrogen, and the best hydrogen is an alkyl halogen; The most preferred alkyl 1 'is present) L' group is not 0 Ja = y (when 1 is a number equal to zero or y + 4 and preferably oF of 11 and preferably + +4 or oxidation state Jain

N = zero preferred; element of the group

AAV

ray I is an element of group V0, 11, or Jia, a group that contains an element of group 104, preferably carbon “carbon silicon” or germanium ¢germanium Y representing an element of group 10 Preferably nitrogen or phosphorus, and the best is nitrogen 'nitrogen Z 0', which represents an element of group 109. It is preferable to nitrogen or phosphorus, 'phosphorus', and the best is nitrogen 'nitrogen L' and 82 represent Each separately a hydrocarbon group containing from 1 to 10 carbon atoms A group containing a hetero-atom of no more than 10 carbon atoms Silicon “5111600” germanium cgermanium Tin lead (dead or phosphorus ye) preferably alkyl C, to C, to Cy alkyl Cs (it has from ? to 51 carbon atoms ¢ (carbon) aryl group aryl or caralkyl and preferably Coo IC C, to Cy alkyl clinear branched or cyclic; most preferably a hydrocarbon group C; to C; to Cs hydrocarbon group Cs 3 may not be present or may represent a hydrocarbon group chydrocarbon group hydrogen vo halogen a group containing a heterotom; Preferably, it should represent a group of linear halah keel; cyclic or branched with 1 to 100 000 carbon atoms and preferably RP not present; or that a hydrogen represents a hydrogen or an alkyl group and more preferably a Jie chydrogen ROR? each separately representing an alkyl group an aryl group a/<a; an aryl group bearing a Y. de gana substituted aryl group an alkyl group an Agila alkyl an alkyl group bearing a “Jia” an alkyl group; A cyclic aralkyl group bearing alternatives or a polycyclic system 0010016” and preferably with no more than 01 carbon atoms, and the best is between 01 and 01 carbon atoms, and the best is also a hydrocarbon group C ; to Min hydrocarbon group Wei to © Arzreal Group C to Cao ANY

1,©; or a group containing © ©, aralkyl ©; or an aralkyl group © to Cy aryl alkyl represents an alkyl group R where PR; heteroatom” for example, and 187 with each other; RY and 82 may bond with each other; and/or may be associated and 8 separately may not exist; or they may represent a hydrogen 1070:0800 group, preferably a chydrocarbyl halogen; heteroatom or alkyl hydrocarbyl group: “carbon” 51 to 1 linear carbon atom; cyclic or branched from the alkyl alkyl de gana and it is preferable that both 8 and 87 not be present; and a group containing an element of hydrogen that is not present; Or it may represent hydrogen BR* containing a hetero-atom. de sana chalogen Group 04 formal charge of the halogen or YZL ligand

A HY) without metal and easy groups entire ligand 771. or 7

X

R' and R' may also be

R*and R' may other. The term “8 and 85 may also be connected to af and mag yo or by combinations of 3 dle and 85 may be connected to each other R*” is meant to be other interconnected. Linear; Or alkyl radicals are alkyl radicals and the alkyl group may be alkyl or cycloalkyl radicals, alkynyl radicals, branched alkenyl radicals, or alkynyl radicals, alkoxy radicals, caroyl radicals Orwell acyl acyl radicals caryl radicals Y. cdialkylamino radicals dialkyl amino radicals alkylthio radicals caryloxy aryloxy radicals caryloxycarbonyl radicals alkoxycarbonyl alkoxycarbonyl calkyl - or dialkyl-carbamoyl adsorbed carbamoyl alkyl- or di-alkyl-carbamoyl caroylamino radicals orylamine cacylamino amino (ad) acyloxy radicals acyloxy radicals

AAY x straight; branched or annular; or a combination thereof. The alkylene group defines alkylene radicals bearing .aryl substituents as an aralkyl group of the following formula: Bd and 87 each separately as an RY group and in a preferred embodiment it is 1 of formula 12

Rt Bf

Rio ph alkyl group © to chydrogen they shade each hydrogen 8 “ JR heterotom” a group containing a heterotom with no more than calla©; to mm linear alkyl or Cyto Cp alkyl and preferably the alkyl group © to ccarbon with a carbon atom of 50 from cbutyl or butyl propyl cethyl ethyl methyl branched; Preferably a methyl group an acyclic group and/or a mixed cyclic group R forming any two ve groups and in a preferred embodiment -aromatic the cyclic groups may be heterocyclic group or propyl cethyl ethyl methyl separately R25 RY methyl group represents every 8th

RY RR” and in a preferred embodiment; The ¢ (isomers including all the Lay) butyl butyl isomers and the 1201hydrogen R® represent the methyl groups of the loam; It represents a group represented by the following form: ROG RY and in a particularly favored embodiment both vo ¥ represents the form . live with? or 2 grate or

T.H.

AAY

VY zirconium preferably zirconium of represents a metal of group M and in this embodiment; -CH,-CH,- RP 5 R' and 7 nitrogen «© p100; Each of the 7 non-existent ones is represented. R75 and 8 thydrogen in particular represent the metallic compound containing a diay element and in a preferred embodiment in the following form: 11 group I compound C CH Ph

SA

J

-phenyl denotes a phenyl group Ph oT and in the compound according to Yo metal compounds containing an element of group ve of the invention are prepared by methods known in the technique such as those described in European Patent No. and US Patent No. 0,888,177 and the references mentioned in the patent ce AQT £04 Al American Invention No. 85,884,174 as they are all mentioned in this statement for reference

CATIYAVA doe Lise for reference. The pending US patent application No. AA cpl 17 describes a gas or slurry phase polymerization process deposited in this release for reference. AX male Cua supported bisamide catalyst

AAV

A preferred direct synthesis of these compounds involves the reaction of the neutral ligand (see e.g. 721 or 7217 of formula 1 or Y with MX, (where M is a metal of the groups to VE and “represents the oxidation state of 5M each da X an anionic group; such as a halide in an enon-coordinating or weakly coordinating solvent ° such as cether ctoluene, xylene, benzene, methylene chloride, and/or hexane in a LAT solvent with a boiling point greater than 00 C; at a temperature of from about 10°C to about 1007°C (preferably from 01 to 1007°C); preferably for ye hour or longer; then treat the mixture with an excess amount (eg, equivalents or more) of KH Jie calkylating agent 0 methyl magnesium bromide in yi gave it The magnesium salts are removed by filtration and the metal complex is separated by standard techniques. contains an element of group 0 by a method involving a neutral ligand reaction; (See eg .721 or 771 os of the form 1 or (Y) with a compound of the form MX, (where M is a metal of the groups ? to Fang) the oxidation state of M and each X being an easily-removable anionic group) in a coordinating or weakly coordinating solvent; at about 07°C or el preferably at a temperature from about 10°C to about 100°C; then treat the mixture with an excess of an alkylating agent; Then extract the metal complex.In a preferred embodiment the solvent has a boiling point of more than 00 C, such as toluene + xylene cbenzene and/or hexane and in another embodiment the solvent includes ether and/or methylene chloride, preferably either A compound of the metallocene type containing a bulky ligand In addition to the metal compound containing a group 10 element the mixed catalytic composition of the present invention also includes a second metal compound, preferably of A metallocene compound containing a large ligand, AAY

Metallocene-type compounds containing massive ddan generally include half and full sandwich compounds containing one or more bulky ligands bonded to at least one metal atom. Metallocene-type compounds with a typical bulky ligand are generally described as containing one or more large 0-ligands and one or more removable groups bonded to at least one metal atom. And in one of my favorite embodiments; At least one of the large ligands is attached to the metal atom by a 1 0-5000©8 bond; It is better to bind with the metal atom by a bond of type 8 # at the site © .n'-bonded. The huge ligands are represented by Gages with one or more rings, or with one or more ring systems 1 open, acyclic. Or merged of fused a combination thereof. These huge ligands are formed; It is preferable to choose the ring (rings) or the annular system (systems) Sale of atoms to choose from groups 1 to 11 of the Periodic Table of Elements 00:6 and it is preferable to choose atoms from the group that consists of carbon Nitrogen 0000860 Oxygen coxygen Silicon sulfur ¢ sulfur Phosphorus 01080100116 Germanium oe boron and aluminum or a combination thereof. It is most preferable that the ring(s) or cyclic system(s) consist of carbon atoms including but not limited to cyclopentadienyl ligands, cyclopentadienyl ligand structures, or a functional ligand structure another similar ligand such as cpentadiene cyclooctatetraendiyl Als Jina) or an imide and preferably choose +0 metal atom from groups ? To 19 and from the lanthanide or actinide series of the periodic table of the elements. It is preferable that the metal be a transition metal from the groups; to OY and preferably from the groups of © and 1 and most preferably the transition metal from group 4. In one embodiment; The catalytic compounds of the metallocene type containing - a massive ligand are represented by the formula: AAY

Vo (11) LL'MQ,

Where M represents a metal atom from the periodic table of elements and may be from groups? to 1".

or from the binary or actinide series of the periodic table of the elements; Preferably, it represents 14 metals

Lilt from the groups ;; © or 6; It is best represented by Lola 138M of Group 4;

5 It is also better if Jiu 14 is zirconium, hafnium, or titanium.

The massive ligands are; (LPy LA is a ring (lila) or open ring system(s);

not annular or fused and are any or ligand system (ila) including ligands

cyclopentadienyl or cyclopentadienyl ligands with or without substituents

of which unsubstituted or substituted, cyclopentadienyl ligands are cyclopentadienyl ligands

cyclopentadienyl 00 carries a substituent of a hetero-atom and/or contains a hetero-atom. It is hoped

Large ligands including but not limited to <cyclopentadienyl ligands

Slay pentafanthrynil cycloadjusted 601216027 ligands Etendenyl 0001 ligatures

cbenzindenyl ligand efluorenyl ligand octahydrofluorenyl ligand lay; coctahydrofluorenyl octatetra indel cyclo 0 pentacyclic ligands

<azulene cazenyl ligands ccyclopentacyclododecene cyclododecene ve

epentalene ligands phosphoyl ligands cphosphoyl ligands phosphinimine ligands

(See International Patent Publication No. VY0 38/6) epyrrolyl ligands

077020171 pyrosolyl ligand carbazolyl ligand borabenzene

and similar; including their <hydrogenated versions, eg ligands

00 tetrahydroindenyl and in one embodiment”; Both *1 and 18 may be phrases

than any other ligand structure capable of binding with 14 © bonds, preferably a ligand of

Type 0 at location © and most preferably an association of type « at location ©. And in another embodiment

as well; The atomic molecular weight (MW) of 1 and 15 may be greater than 01

an atomic mass unit (a.m.u.) atomic mass unit; Preferably greater than © atomic mass unit. And in

ve another embodiment; “*1 and 1 may contain one hetero-atom or “JST” for example; nitrogen

AAY

Va

Nitrogen, silicon, boron, germanium, sulfur, and phosphorus 000:05 in combination with carbon atoms to form a ring or an open ring system. acyclic or preferably built-in: ; For example, an additional scrambled cyclopentadienyl ligand ©M10©©-16160. LA and 1 may also be other bulky ligands including but not limited to camides and phosphides calkoxides aryloxides caryloxides imides 01088 Carbolides ccarbolides borollides porphyrins phthalocyanines corrins and other -polyazomacrocycles 1' and 15' separately represent identical or different types of a large ligand attached to 34. In one embodiment; be only one of +1 or L®

1 is of the form (I) and LY and 15 separately may carry Son from a combination of the alternate “## combinations or may be devoid of them. Examples of substituent R groups include but are not limited to one or more substituents chosen from the group consisting of chydrogen hydrogens or linear alkyl anal radicals; or branched; or alkenyl radicals calkynyl radicals “cycloalkyl” or ve aryl radicals; acyl radicals caroyl radicals calkoxy radicals caryloxy radicals alkyl thiomne 1 and al; AD alkyl amino radicals “dialkylamino” alkoxycarbonyl radicals caryloxycarbonyl radicals carbamoyl 0 mono or dialkylcarbamoyl - nuclei; acyloxy radicals cacylamino radicals caroylamino radicals linear alkylene radicals; x is branched, toroidal, or a combination thereof. In a preferred embodiment; The substituent R groups contain no more than 0 5 atoms other than chydrogen, preferably from 1 to yo a carbon atom, as they may also carry substituents of halogens, hetero-atoms, or the like. Examples of alkyl substituents R R include but are not limited to cethyl propyl methyl groups butyl butyl pentyl hexyl cyclopentyl Yo hexyl cyclohexyl benzyl or phenyl and the like; Including all of his colleagues

AAY

For example, tert-butyl, cisopropyl, and the like. Other hydrocarbyl radicals include; Organometalloid radicals bearing Shy from fluoromethyl Jie fluoroethyl difluoroethyl iodopropyl bromohexyl chlorobenzyl ° chydrocarbyl including ctrimethylsilyl ctrimethylgermyl methyldiethylsilyl and the like; and semi-metallic organic radicals bearing Shy from halocarbyl including tri(trifluoromethyl)-silyl methyl-difluoromethyl silyl-(trifluoromethyl)-silyl silane A BJ fag ag cmethyl- bis(difluoromethyl)silyl bromomethyldimethylgermyl ve and the like; Boron radicals bear two disubstitiuted boron including dimethylboron for example; Nectogen roots bearing two disubstituted pnictogen including dimethylamine dimethylphosphine dimethylphosphine Jd amine diphenylamine J wd emethylphenylphosphine and chalcogen radicals including ¢methoxy ethoxy Ss) vo propoxy (0:0:0; phenoxy methylsulfide and ethylsulfide. Non-hydrogen substituents R R include carbon atoms ccarbon Silicon, boron, aluminum, nitrogen, p0, phosphorous, oxygen, coxygen, tin, sulfur, germanium, and the like, including but not limited to olefins, Y. olefincally unsaturated substituents include cvinyl-terminated ligands eg biotinyl 9 ( cbut-3-enyl propenyl ) Y ( ¢prop-2-enyl hexenyl 0 hex-5-enyl and the like. Also, at least two “groups” are connected, and preferably two adjacent R groups, to form a ring structure of which ? To 510 atoms choose from carbon, nitrogen, oxygen, coxygen, phosphorous Yo, silicon, esilicon, germanium, aluminum, caluminum, boron 50:08 or a combination of AAY

VA

Substitute 1-butanyl lyatoweb-1 sigma carbon bond as R thereof. like that; 14. It may form a group with the metal carbon sigma bond such as one easily removable group on MHI and other ligands may bond with the unstable ligand of the lower Q single anion; It is denoted by 0. In one embodiment, the oxidation of the metal Ala by a sigma bond. And depending on M associated with a monoanionic labile ligand ° above a neutral catalytic compound of (IT) or ¥ so that formula 1 represents the value of “ is equal to zero; for a metallocene type that contains a bulky ligand. weak bases Examples of ligands include, but are not limited to, carboxylates carboxylates cethers ethers phosphines camines amines ccarbon carbon atom Yo to 1 in it from hydrocarbyl Hydrocarbyl sda «dienes dienes 1 form two bonds or AT halogens and the like or a combination thereof. In the chydride embodiment other hydrides those Q over © are part of a compact ring or compact ring system. Examples of coyclobutyl ligands of the substituents of L described above include ctrifluoromethyl radicals, cheptyl cyclohexyl cmethylidene ¢pentamethylene pentamethylene ctetramethylene vo phenoxy («01600; di(:<-methyl anylide) propoxy cethyoxy ethoxy “methyoxy dimethylphosphide) cdimethylphosphide (0nf00n; dimethylamide) and the like. In one embodiment, catalytic compounds of the metallocene type containing 15 bridged LA where (IM) of the invention include such compounds of the formula Gig have a large ligand ov. One “JY” denotes bridging group to each other through a bridge group 0 so that the formula is represented by the following A to it (IV) L*ALPMQ, defined as catalytic compounds (IV) and these bridge-bound compounds are represented by the formula and hand ML? bridge-linked metallocene type containing a large ligand.

AAY

As defined above. Examples of A bridge group include but are not limited to bridge groups containing at least one atom of groups 11 to OT often referred to as a divalent moiety such as but not limited to at least one atom of 010080 Silicon, carbon, oxygen, coxygen, aluminum, boron, germanium, tin, or a combination thereof. It is preferable that the bridge group A contains a carbon atom, silicon, or cgermanium, and it is more preferable that A contains at least one atom of silicon or carbon 08:500. An M bridge group may also contain substituent R groups as defined above, including halogens and iron. Examples of an M bridge group include

1 to name a few 80:0; RSH 8/058/751; 8:08 Cus (RP 8 separately represents a radical group that may be a hydride chydrocarbyl hydrocarbyl bearing “Ja chalocarbyl halocarbyl bearing substituents; Semi-metallic organic group bearing Sha of chydrocarbyl hydrocarbyl Organic semi-metallic group bearing halocarbyl substituent boron

vo 0 carries two substituents” pnictogen carries two substituents; A chalcogen carries two substituents or halogens or two or more groups of 8 may be linked to form a ring or ring system. In one embodiment; Bridge-linked metallocene-type catalysts containing a massive ligand Aled of formula (IV) may contain two or more M-bridge groups (see Patent 81 European No. 700 (TEE)

y. In one embodiment; Metallocene catalytic compounds containing a massive ligand include those in which the © substituents on the massive ligands +1 and 15 represented by formulas (TI) and (IV) carry a number of Silas or Lisa substituents on each huge ligature. In another embodiment the large ligands LA and 1 represented by formulas (mn) and (Iv) differ from each other.

AAY

Y. The catalytic compounds of the metallocene type and other catalyst systems containing a large ligand suitable for use in the invention include those described in US patents.

O, AOA RY, TARF for the year, AOA RY, TARF for the year, YY for the TARF, 1 H, TARF, LARF 6 5 and international patent publications according to the Treaty of 0,474,007 5 8,5,1 (0,A08,1 0A

A/a Er Cooperation in the Field of Patents No. 1 Tattam./TT>>Nd/RT Publications 1771/14>Amaagi. Right TFA 090 (A= OVA AVA European Patent Nos. - YOY 445 R BI=+ L (BI=« ITY with both AYE except for the words to swear 0 as they are all mentioned in This statement in its entirety is for reference. (BIL) In one embodiment, metallocene-type catalytic compounds containing a bulky ligand useful in the invention include bridge-bound metallocene-type compounds containing a hetero-atom and a single bulky ligand. Examples are described These types of catalysts for the Lily Treaty and catalytic systems; for example; in international patent publications. YY. To 4. Honor 107 1// AH 0,Y14,£40,50,YYV, 664 Lad in the archives of the archives, the shelves of the racks of the shelves, not 1/6, as they were all mentioned in Am EY EY and the Patent Bulletin This statement is cited in full for reference. © In this embodiment, the catalytic compound of the metallocene type containing a bulky ligand is of the formula: (V) LAMQ, selected from group 3B or 11 DY represents a metal atom of groups M Cua and the lanthanides of the periodic table of the elements; It is preferable that l represents a transition metal from the vo groups

AAY

transition from group 4; © or 6; most preferably TIM and preferably VY; to ttitanium a glSO and in particular 0 of the group; In any oxidation state QED THB M represents M with Wai ye J and is IM and represents “1 large ligand with or without substitutions associated with

Ac sara A An additional ligand with a hetero-atom; is represented by J and m is associated with 14 and 1; It represents an integer equal to Tose, and it represents a funivalent inflection; A monovalent anionic ligand ©m and 1 represents a combined ring system. and in an embodiment; CLE or 7. and in formula (7) above; forms 1 ia and 0 of the form (7) as 14 A of the form (7) as defined above for *1; And LO is (Im) above in formula 18) an element with a Jin number] a ligand containing a hetero-atom where (V) is of the form J and represents or an element with a coordinating number of 11 years old Choose from the group coordination number 1 of the periodic table of elements. It is preferable that it contains [1 atom “chosen from group Y or sulfur from 6n” and the best is oxygen (phosphorus) and in an embodiment of the invention; Contains a massive ligand that is complexes of scrambled cyclic ligands that include the massive ligand; ring(s) or cyclic cua heterocyclic ligand complexes(s); one or more hetero-atoms or combinations thereof. Examples include hetero-atoms Nitrogen VT is preferred to 11, for example, but not limited to, an element of the groups: aluminum, aluminum, coxygen, oxygen, sulfur, sulfur, boron, boron ¢nitrogen, these compounds are 4 Bd and .tin and tin are described. phosphorous “silicon + catalyst of the metallocene type containing a bulky ligand in patent publications 175483/44 and patent AY/IVFVA 35/9 4071 45/717707 4071 INT.

OY, TT and US Patent No. 1-0 AVE 005 European No.

Come

AAY

YY

In one embodiment; The catalytic compounds of the metallocene type that contain a large ligand are those complexes known as transition metal catalysts based on double ligands such as those described in quinoline or pyridine serrations containing pyridine moieties; M1 49748 deposited in Jun 77 vA) YY US Patent Application Serial No. 0 and US Patent No. 1,003,127 filed Aug 11; 1000 AD, where I mentioned the AOU in this statement as a reference. In the GAT embodiment metallocene catalytic compounds containing bulk ligands include those described in Gay's international patent publications PCT No. 99/001441 and No. 58/477154 which are cited in full herein by reference. 1 and in a preferred embodiment; The catalytic compound of the metallocene type that contains a large ligand is a “Gl preferably transition metal” complex of the large ligand; Preferably a picbonded sb bonded ligand bearing substituents or devoid of a Jl terminator and one or more heteroallyl moieties such as those described in US Patents No. 57, No. /A07,© No. 2,759,505 and European Patent No. OV 7305 51-0 where they are all mentioned in this statement in full for reference. and in a particularly favorable embodiment; The other metallic compound or the second metallic compound is the catalytic compound of the metallocene type that contains a large ligand and is represented by the formula: (v1) L°MQy(YZ)X, © where M represents a metal from the groups? to 10; preferably a transition metal of the groups; to VY and most preferably a transition metal of groups of 0 or 6; 17 represents a bulky ligand associated with tM and each © bonds separately with M and forms (0:077 ligand; a single-charge multi-dentate ligand is preferred Ay funicharged or © represents a monovalent anion ligand also bonded with EM and Jip a univalent anion group when Y = n or X represents a group “| divalent anion =n Lae divalent 1; and “ is equal to 1 or .1 AAY

Yr and 0 as defined (I) above in the form Wie. 1 and 14 as o(VI) and in the form - -j08- and ¢-NR- ¢-0- from the set formed by Q above in formula (111); It is preferable to choose the word 51 t yatang (NR; -OR -5; 7 represents © or 5; and 7 is chosen from the group consisting of

NR- represents Q and AH aryl groups carry substituents or do not have a terminator provided that when -11 “PR, and 11-; and selects -PR; ¢-SiR; 88 «NR; ¢-OR the 7 chooses from the group consisting of + nitrogen esilicon silicon ccarbon from a carbon-containing group R a hydrocarbon group R preferably when representing sphosphorus and/or phosphorous oxygen Oxygen and most preferably a carbon alkyl group Ys to 1 carbon atom has from hydrocarbon group to ?; 1 integer ranging from Tae and “representing taryl or aryl ceycloalkyl cycloalkyl alkyl

X or ?; The * represents a monovalent anionic group when 8 equals ? or 1 preferably equal to 0 representing a divalent anionic group when « equals 1; * Preferably represents the carbamate moiety or any other mixed allyl moiety described by the combination of a carboxylate carbamate and 2.7 Q and in a particularly preferred embodiment represents the compound of the metallocene type containing a ligand Massive with the form: © pL 1 = “Ta Sn m 5 7 khik< f lgst CH,

CH; activation and methods of activation Activator The catalytic compounds described in this statement are preferably mixed with one or more olefin activators to form a catalytic system for olefin + polymerization.

AAY

For the purposes of this patent specification and the accompanying claims; The term 'activator' means any compound, component or method capable of activating any of the CLS yall catalysts of the metallocene type containing a massive ligand and/or metallic compounds containing an element of the group Gy 11 of the invention > These activators may include, but are not limited to, a Lewis acid, a non-coordinating ionic activator, an ionizing activator, or any other Lay compound including Lewis bases Caluminum alkyls Cocatalysts Cocatalysts of the traditional type and combinations thereof that can convert the neutral catalytic compound of the metallocene type that contains a large ligand or the metal compound that contains an element from group 101 to a Jad cation catalytically catalytically active cation of a metal compound containing rae of group 15 or a cation of a catalytic compound of the metallocene type containing a bulky ligand.The scope of this invention is to use alumoxane (jus ga olf) or a modified alumoxane as a stimulant” and/or the use of “ad” ionizing activators, whether neutral or ionic; Jie quaternary (pentafluorophenyl) boron thalathi (p-butyl) ammonium tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron Vo or a metalloid precursor from Pk perffluoro Jd boron trisperfluorophenyl boron or a semi-metallic source of ctrisperfluoronaphthyl boron polyhalogenated heteroborane anions (see International Pat. contains a massive ligand and/or a metallic compound containing an element of group .10# and in one embodiment; An activation method is also used that uses ionic compounds that do not have an active proton but are capable of producing a cation of a metal compound containing an element of group 11 or a cation of a metallocene catalytic compound of the type ve containing a large ligand, as well as the inactive anion. its coordinator; And it's described in my innocence

ANY

Yo and Patent Ame OVY 407 European Invention No. 6797 4736 M 0 and No. 18, FAY, OTA are all mentioned in this statement for reference. 5 alumoxane compounds There are various ways to prepare alumoxane but not limited to those described in the patents Leia Modified; 85 rk rack 34 (0,Y.1,144 (0,0 4),¥0Y (£,90Y,0¢ + ARFTARK) American A numbers 0 Arrah Tarf (0, FAAS Karak Al Takhtarik ETF Kalaz Karak AVE VTS (0,791,074 Bahr Al Raf Al Raf Al Narf Larf Raf Arf Anqarf Harf Tarf Tarif Tarif Tarif Tarf Tahar Qarif) (O, VF), YOY “Ugh in 0 OT) EV and European Patent Publications No. 0,474, YET 5 7

Gay and International Patent Bulletin 31-6 OAT and A=09% 716 burn 174 3 Ve of Patent Cooperation Treaty No. 101860/14 which are all cited herein in full for reference. It is suitable as stimulants Organoaluminum compounds organic a sti ll Compounds include ISO ON ctriethylaluminum ctrimethylaluminum tri-n-hexylaluminum tri-n-hexylaluminum ctriisobutylaluminum butylaluminum vo and the like. tri-n-octylaluminum tri-n-octylaluminum paired with AT or a specific cation clad and ionizing compounds may contain the proton of the remaining ion of the ionizing compound but not coordinately bonded with him or linked with him symmetrically only. Such compounds and their methylates have been described in ALE publications with a degree of F. TVO solution, European Patent Nos. YYY stone. deposited in? August"; 9941 AD; They are all mentioned in this statement in full for reference

AAY

A

Other activators include those described in IPC 98/078515 as Lela YY OY trifluorodifluoroaluminate (tris (2,2',2)-nonafluorobiphenyl (fluoroaluminate) and this publication is cited in full herein for reference. Combinations of activators alumoxanes are also included in the invention; for example a combination of alumoxanes 0 and ionizing activators; see for example EP No. 07 00 /7 + 31 and Bay's two IPC publications Patent No. 94/097974 and No. 90/146044 and US Patents No. 80,107,101 and No. 05,507,4 are all mentioned in this release in form 098997/98 cited herein for reference describes the activation of large ligand-containing metallocene catalysts using perchlorates periodates and iodate 1008:68 Including its aqueous forms hydrates and describes the two publications of the two international patents No. ATTY and No. AAT CTY mentioned for reference using SEY oY) -bisphenylditrimethylsilicate) 4THF 4THF. As an activator of the catalytic compound of the metallocene type, which contains a large ligand. The International Patent Bulletin No. 181770/99 cited in this statement for reference specifies the use of organoboron-aluminum acitivators. European Patent No. 7949 VAY 81-0 describes the use of psyllium salt. Silylium salt in combination with a compatible non-coordination anion. like that; The invention includes Gy da Coad for such activation as the use of radiation (see EP No. 481 115 81-0 Cus cited in this statement for reference); electrochemical oxidation and the like as activation methods with the aim of making a neutral catalytic compound of the metallocene type that contains a massive ligand or an olefins cation source for a compound of the metallocene type that contains a massive ligand capable of polymerizing olefins ve

AAY

Yv activators or other methods for the activation of a metallocene catalytic compound of type a containing a large ligand in for example are described in US Patent No. Pentafluorophyllite (3%) SL) 343/17 43597 No. 8/77 purane)benzimidazolid) octadecylmethylammonium 0 ; Where ((dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide) is mentioned in this statement for reference as a reference. The possibility of mixing metallic compounds containing Lad and within the scope of this invention described above and catalytic compounds of the metallocene type Alc V0 is an element of the group containing a bulk ligand with one or more catalytic compounds represented by formulas using one or more activators and one or more activating methods described (VI) to (mm) above. That any of the catalytic compounds of type Lad and within the scope of the invention one of the fluoride of the invention contains metallocene ly fluoride containing at least one massive ligand as described in the least fluorine or an easily removable group contain 0s fluorine

Wo Filed 191.9176/09 US Patent Pending Serial No. November 4978 M. In a preferred embodiment the modified alumoxane 065 is mixed with the two compounds.

MMAO3A of the invention to form a catalytic system. In a preferred embodiment Gay mixes the first and second metals commercially available from cheptane into modified methyl alumoxane (LS ga sl) heptane

Modified Netherlands under the trade name Akzo Chemicals, Inc. Akzo Chemicals, Inc. These aluminoxanes see for example the aluminoxanes (Methylalumoxane type 3A where mentioned in this statement £ 00.0), 0A8 described in US Patent No. for reference ) with the first and second metal compounds to form a catalyst system

AAY

Ya

It ranges from molar ratios 4d ge, and the first and second metal compounds can be mixed in different ratios.

Nerd to 40:01 preferably V9 to 995:1 preferable NY eee to 0011 60:46”; Better than 1:70 to 701:30 Better than Yea to 80:71 Better than desirable and/or end product The exact ratio chosen depends on the final product Eee to Instrument method Activation 0 and 7; 1 in the forms Gr Bad) and in a special embodiment; When using the two preferred metal compounds; based on weight percents of activators with the same stimulant; The weight percentages range from csupport the weight of the two metal compounds and not based on the weight of the activator or any carrier material oF by weight for the compound in formula 7400 and from © to 1 to 7948 by weight for the compound in formula 01 of by weight For compound Zoe to 01 and 1 to 7960 by weight for compound of formula 00 preferably 7701 to Ee and 1 to 7860 by weight for compound of formula 61 and better than oF of formula 1 by weight of the compound of formula 7. In a particularly preferred embodiment the compound of formula is agitated and then mixed with the compound of formula ¥ and then emethylalumoxane using methylalumoxane is injected into the reactor. 1 In a particular embodiment; When compound 1 and ethinyl tripiphalate Ve are used both are activated using the same activator; Cua indenyl zirconium tris-pivalate is the preferred weight percentage; based on the weight of the catalysts; and not on the basis of the weight of the activator to 7485 by weight of the compound] and from © to 79880 by weight 01 or any carrier; Ranging from 7980 to 00 preferably from cindenyl zirconium tris-pivalate to cindenyl zirconium tris-pivalate by weight to indenyl zirconium tris-piphalate 750 to 01 by weight for compound 1 and from © to Ee by weight of compound 1 and from ZA to 01 and preferably of cindenyl zirconium tris-pivalate and in an embodiment of indenyl zirconium tris-pivalate by weight of indenyl zirconium tris-pivalate. The zirconium is then injected into the T and then mixed with the compound cmethylalumoxane using the methyl alumoxane reactor. Yo

AAY

Ya

VI een The mixed metal compounds and the activator are mixed in proportions ranging from about La sas to about 0:00. And for Vi) about 1:00 to about that Ja dg .z—1)... caluminates aluminates borates cboranes for borane compounds and for alkyl aluminum compounds (such as 0:01 to about 0:1 (the ratio ranges from about 0 mixed with water) preferably diethylaluminum chloride

Ae to about 0:09 ratio of about conventional type catalytic systems may be mixed with Formulas 1 and 11 of the present invention on the metallic compound of which Gi the mixed catalytic composition may contain a group 10 element as described above; and successively on a conventional-type transition catalyst. Al-type) and transition metal catalysts of the conventional type include those known as Phillips-type, vanadium-Ziegler-type catalysts, and vanadium catalysts. Examples of Ziegler-Natta catalysts are well described in the JO book. For example, the John Boor edition of 'Ziegler-Natta Catalysts and Polymerizations' titled vo

Abd Also Described a) AVA New York cAcademic Press Traditional Type Transition Metal Catalysts in US Patent Nos. tar etc. cE VY, YAY (£,006,000 per 40¢ per There is no trace of the above and 5,475,741, all of which are mentioned in this statement in full for reference, and include transition metal catalytic compounds of the conventional type that can be used in this invention. OV present transition metal compounds from the groups “to” of the periodic table of the elements. 1 to these transition metal catalysts of the conventional type with the formula: +108 where JTS and groups may be preferred; to ©; and the best OY represents a metal chosen from groups “ to M halogen atom or group JAR titanium titanium Dads group 4; more Yo

AAY

b: chydrocarbyloxy and “represents the oxidation state of MU.” 8 examples include, but are not limited to, “calkoxy,” phenoxy bromide, chloride, and fluoride. Examples of transition metal catalysts include: The conventional type where das M is titanium but not limited to “Ti(OC,Hs)Cly “Ti(OC,Hs);Cl” TiBry ¢TiCly

“Ti(OC,H;),Br,” “Ti(OC3H;5),Cl,” “Ti(OC4Hy),5Cl ° panel 110.1/3 and 11)00. Transition metal catalytic compounds of the conventional type based on electron-donor complexes of 028065:000 magnesium/titanium useful in the invention are described; For example; In the two US Patents No. 07,95159; And No. 7 where they are mentioned in this statement in full for reference. It is considered derived

Clad), 1 ethyl MgTiClg(ethyl acetate) is particularly preferred. It describes UK Patent Application No. 5 7,015,725 and US Patent No. 8,7117,07 as they are cited in this statement for reference Various conventional-type catalysts containing vanadium Examples of conventional-type catalysts that contain vanadium include, but are not limited to, vanadyl trihalide, alkoxy halides and vanadyl trihalides (Jbl). alkoxides such as VOCL(OBu) “VOC; where Bu is butyl and:(:70)0©011; vanadium tetra-halide and VCl, fie vanadium alkoxy halides and (701:)08; vanadium and vanadyl acetyl acetonates and chloroacetyl acetonates + as V(AcAc); and VOCL(AcAc) where (AcAc) Acetyl acetonate is represented by acetonate AHH 2. It includes catalytic compounds of the traditional type that contain vanadium preferably ¢VOCl; 1701 and VOCL-OR where Jie R is a chydrocarbon radical and an aliphatic hydrocarbon radical is preferred or aromatic to Cio aliphatic or aromatic hydrocarbon radical m to © as ethyl phenyl© isopropyl cisopropyl butyl propyl p-butyl n-butyl Isobutyl

AAY

50-01 ctertiary-butyl chexyl cyclohexyl “cyclohexyl naphthyl...<naphthyl etc.; and vanadium acetyl acetonates. Examples include SUS je chromium catalyst compounds of the conventional type; Often referred to as “Phillips-type catalysts (ula) which are suitable for use in this present invention”CrO; ,Cly) chromyl chloride 7-ethyl chromium hexanoate Jind «chromium-2-ethyl-hexanoate chromium acetylacetonate ¢(Cr(AcAc);) and the like. Unspecified examples are described in US patents AMAC LELARKT NUMBERS 4408 (FLV QFRA KARK 19 AR AND 4 RALA 1) WHERE 0 THIS STATEMENT IS INTENTIONED IN ENTIRE FOR REFERENCE. Other conventional transition metal catalytic compounds and catalyst systems suitable for use in the present invention are described in US patents Lam Tark numbers Y,000 Arfak Tevert Ark (FV, TY) Flare Lark Gallart Tarf Karf Demara Qarf 6 Arat Garf 51746 9,89 and 0,819,859 and European patent No. 4816 4135 0-2m and No. 4771 470 0 -1; Cam are all mentioned in this statement for reference. Other catalysts may include cationic catalysts ACT Jie and other catalysts of iron cobalt “0n; nickel and palladium are known faa in Technology. hil eg US Patents 41/117 EAT, AVE 6, EVY,009 >< f/a 188,47,; They are all mentioned in this statement for reference. usually; Conventional transition metal catalysts activate these; Except for some compounds of conventional-type chromium catalysts using one or more conventional-type co-catalysts described below. Transition metal catalysts of the conventional type may also be activated using the activators described above in this patent specification as ve been realized by those familiar with the technique. ANY

YY

The conventional type transition metal catalytic compounds shown above may have the formula MM WX Rye where MP represents a metal chosen from groups 1 to © and 71 to 17 of the periodic table of elements; Me is a metal from group 1 of the periodic table of elements; vig represents Tae equals zero or 1, and each 2 represents 0 any halogen atom; and represents a number ranging from zero to ?; Each BB is a monovalent hydrocarbon radical or by hydrogen representing a number from 1 to ;; Where 5 minus c equals at least 1. Compounds of conventional-type organometallic co-catalysts other than the above-mentioned conventional-type transition metal catalysts have the formula Cua MPR, 149 representing a metal selected from groups IB IA JA or ITA such as lithium dlithium sodium 1 ¢ beryllium barium cbarium boron <boron aluminum annealed zinc zine cadmium gallium sa; ks equals YO) or ?; by valency which in turn usually depends on the specific group to which the MP belongs and each 83 represents any monovalent hydrocarbon radical. Examples of conventional-type organometallic co-catalysts vo that are suitable for use with the conventional-type catalysts described above include but are not limited to emethyllithium cbutyllithium dihexylmercury U5 gu cdihexylmercury magnesium SU cbutylmagnesium diethylcadmium Jo potassium cbenzylpotassium diethyl zinc cdiethylzine tri-n-butylaluminum isobutyl boron J diisobutyl ethylboron di Y. Cdiethyl cadmium, di-n-butylzine, and tri-p-amylboron, ciri-n-amylboron, especially alkyl aluminum compounds ctri-hexylaluminum frame 16; Trimethylaluminum and triisobutylaluminum. Other conventional co-catalysts include mono-organohalides VO, hydrides of oY group metals, and mono- or binary halides

AAY rr

AT metals of the two groups? and hydrides and hydrides of mono- or di-organohalides of the organic radical. Examples of co-catalyst compounds of such a conventional type include, for example, di-isobutylaluminum bromide (HD) bromide. Methyl magnesium chloride cisobutylboron dichloride isobutylboron chloride cethylberyllium chloride ethyl beryllium chloride cmethyl magnesium chloride cethylcalcium bromide ethyl calcium hydrate ¢methylcadmium hydride cadmium Jie di-isobutylaluminum hydride chexylberyllium hydride cdiethylboron hydride ethyl boron octylmagnesium hydride dipropylboron hydride propyl boron (ES) dichlorohydride cbutyl zine hydride coctylmagnesium 1 ¢ “di-bromo-aluminum hydride” dichloroboron hydride Boron Metal co-catalyst compounds -bromocadmium hydride and organic bromocadmium hydride of the conventional type are known to those versed in the technique and provide a fuller search About these where they mentioned 0,0 AY, 610 and No. 7,7710007 compounds in the two American patents No. “. In this statement in full for reference to them for reference. Polymerization process Metallic compounds are; The mixed metal compounds and catalyst systems described above are suitable for use in any polymerization process; Including operations carried out in a 501:00 solution” in a gaseous or slurry phase or a combination thereof. It is preferable that the polymerization process be a single process; The most preferred gaseous or slurry phase Jolie phase reactor and the best process using a single gaseous ©. Preferred; The catalyst system consists of metal compounds (the catalyst) and/or the activator at the end (the co-catalyst) introduced into the reactor as a solution. Toluene solutions are prepared as a suitable alkane such as a metal solvent by dissolving the catalyst in any solvent that poisons, etc. may affect. The solvent can first be purified to remove any toxins

AAY

Ye and/or trace water oxygenated compounds in catalyst activity; Including any trace amount of water as an Lgl-activator, the solvent can be purified by, for example, using oxygenated compounds as an activator. It is preferable to dissolve J gana copper and an activated alumina copper catalyst, and the homogeneous solution of the catalyst can be completely dissolved in the solution to form a homogeneous solution, both catalysts in the same solvent as desired. Once the catalysts are dissolved in the solution; it is 0 that can be stored until it is used. With regard to the polymerization process; It is preferable to mix the catalyst with an activator before introducing it into the reactor. Others to solutions of reactants In addition; Other solvents and reactants may be added to the activated catalyst (on-line or off-line) or to the activated catalyst or catalysts. See US Patents No. - © Ae OF AY and European Patent No. <0, TAYYYY _and No. 2,7 mentioned in this statement in full for reference Cum 497/47594 International Patent No.

Ady to the reactor. solution feed systems for reference; Several different configurations are possible for mixing catalysts and activator. The vo system may include metal compounds and/or activator to the reactor in solution and in one or more lee. Metallic compounds can be activated separately; In series or as pentane alkane embodiments a solution of the two activated metal compounds is introduced into an alkane $d or similar to an isopentane reactor ctoluene hexane hexane “pentane gaseous or slurry phase. In another embodiment the system of catalysts or components may be introduced into the reactor and in one embodiment; The compound comes into contact with an emulsion or suspension as a modified sv suspension; in a solvent and before the second metal methylalumoxane with the activator; such as methylalumoxane solution feeding to a gas phase reactor; directly slurry or lotion. The solution of the compound is mixed with the solution of the second compound, the activator, and the metal 11 that contains an element from the group, and then it is introduced into the reactor.

Yo

ANY vo and in one embodiment; This invention is directed towards polymerization or copolymerization reactions, preferably carbon with a carbon atom Vo, one or more monomers with ? to a monomer incorporating the polymerization of carbon 8:000. SIA is considered the best of? to ccarbon carbon atom VY from ? to in particular for copolymerization reactions involving monomer polymerization fan The invention is appropriate NetWeb-1 propylene monomer: M cethylene one or more ethylene olefin monomer olefin 0 Niske-1 0601606-1; 4-methyl-01-pentene-ad-and-al-obeta-4; Nitko-1 chexene-l or cyclic olefins and cyclic olefins 3,5,5-trimethyl-hexene-1 nesca-01-methyl So oY diolefins vinyl diolefins a combination thereof. Other monomers may include vinyl monomers Polyconjugates 00176066 Norbornene edienes such as © cethylene turbonadiene diene monomers ©00:00080:©0. It is preferable to produce a copolymer of ethylene < norbornene with at least one alpha-olefin where the copolymer is an alpha-olefin 000 carbon atoms and better than 11 ? to 55010 carbon «00»»» preferably from; to and in -carbon 1 carbon atoms of ; to Shain and more to carbon; to 4 carbons Alternate embodiment; Twin-substituted olefins described in International Patent Publication No. 797104/98 can be copolymerized or copolymerized by applying the invention described herein.

In another embodiment ethylene or propylene polymerizes with at least two different co-monomers to form a terpolymer and the co-monomers are » - the preferred being a combination of alpha-olefin monomers having from 4 to 10 atoms carbon 000: e; and better than; to INA a carbon with optionally at least one diene monomer. Preferred tertiary polymers include combinations such as ethylene [butene-1-nitweb-1] [ethylene 1-hexene 1p-ethylene atha/propylene] cbutene-l (ub sa—) [propylene propylene 1 [ethylene (uliY/propylene - chexene-l-hexene

Yo propylene (lus sill ethylene / norbornene) and the like.

AAY

In a particularly preferred embodiment the process according to the invention relates to the polymerization of ethylene and at least one co-monomer thereof of ; to 48 carbon atoms 08:00; preferably from; to 1 carbon atoms 8:000. In form (ala) the monomers include 1-cbutene-1-methyl-1-pentene [4-methyl-pentene-] hexene-l and 1-coctene-l and 1- Butene-1 nitweb-1 Ss hexene-1 ° is the most preferred.Usually, a continuous cycle is used in a gas-phase polymerization process where in one section of the reaction system cycle a gaseous cycling stream is heated. The gas stream, also known as the medium recycle stream or the “fluidizing medium,” is generated in the reactor by the heat generated from the polymerization process. This heat is removed from the recycled composition in the AT section of the cycle by means of a cooling system. Cooling system located outside the reactor Clases A gas stream containing one or more monomers circulates continuously in a gas fluidized bed process to produce polymers; through a fluidized bed in the presence of a catalyst under reactive conditions The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor.At the same time, the polymer product is withdrawn from the reactor and a new monomer is added to replace the polymerized monomer (see for example US Patent No. 44 Dr. Prices are higher. for reference). hmm) to about 4544© kPa (+0 lb/in” standard); preferably in the range from about 10 001 kPa (lb/in standard) to about 77054 kPa (04 lb/lb standard); preferably in the range from about 174 kPa (You lb/in) to about 7754 kPa (40 lb/in Standard); AAY vv kPa (750 psi' standard) to about 1774 and the best in the range from about psi' standard). To) ?? 064 kilopascals in the process that is forced into the reactor temperature, and the temperature of the gaseous reactor may vary from about 17 C to about 1707 C, preferably from about 1 C to about sh C; and most favored in the range from 0011 from about 70m to sad) um; and best in 11#0+ temperature change polymerization as AIX M. 7001 can be about 65m to about, to change the properties of the final polymeric product. The monomer has partial pressure. The productivity of the catalyst or the catalyst system is influenced by the partial pressure preferred for the main ethylene monomer, mole percent. The molar percentage ranges 790 to Yo from about cethylene or propylene ©«2160 C:0» ethylene is preferred 1 lb / y' (YO) kPa ©0117 in mol and the partial pressure of the monomer ranges from about lbs" Ye) to about 70 164 kPa ((psia) pound/inch? absolute); these are typical conditions in a gas-phase polymerization process. In one of 11597 to 19017 Approximately aethylene embodiments The partial pressure of ethylene ranges from (:5 m).

Neo A to Vio in the reactor from ethylene to ethylene hexene molar ratio of hexene and in a preferred embodiment; The reactor used in the present invention and process according to (Ibs) pounds lb © + +) (kg/hr) kilogram/hour of the invention yields over 7177? kg/hr (lb/hr) or more than 1,000,000 (polymer per hour) to about 09,060 kg/hr (lb/hr); the best is more than 10001 (polymer; preferably over £00 kg/hr © 11101 kg/hr lb/hr); Better yet, more than 00001 (kg/hr 6 min 500 kgh yp A lb/hr); Even better is Youu (lbs/hr); The best is also more than 717,700 kg/h (Youu) of 000? kg/hr (GE ~ lb/hr) and most preferably PN (lb/hr). 000001 (lb/hr) to more than £000 kg/hr (15001 vs.

ANY

Ya

Among the other processes that take place in the gaseous phase included in this process of invention are 6l, llara 50,510, AVA 7r / a17 rf 47 ald J described in US patents

Horo ANY 017, VRE 000 and European Patent Publication Nos. are all mentioned in this statement in full for reference. Cum 8-4 1 Generally a slurry-phase polymerization process uses pressures in the range of about that and temperatures in the range from el through atmospheres to about 00 atm m. In a slurry-phase polymerization process, 0171 C to about ial is formed in a solid particulate polymer suspension of solid particulate polymer and ethylene monomers, to which ethylene liquid polymerization diluent medium is added. Often with a catalyst. The suspension comprising the co-hydrogen and the hydrogen-diluent is removed from the reactor intermittently or continuously as the volatile components are “distillation” from the polymer and recycled; Optionally after distillation volatile components reactor. The liquid diluent used in the polymerization medium is usually a branched alkane. It should be an alkane, preferably ccarbon, an ANY carbon in it? to an alkane relatively. When a propane Sala 5 media is used as a liquid media under vo polymerization conditions, the process should be operated at a temperature and pressure higher than the critical propane temperature of the diluent in the reaction. Preferably using critical temperature and pressure or isobutane sticky:1.hexane medium of the invention polymerization as Gy and in one embodiment; A preferred polymerization technique or slurry-phase process is indicated; It maintains particle form polymerization particles + temperature at a lower value than the temperature at which the polymer turns into solution. A technique like this is well known in the technique; It is described, for example, in US Patent No. 7,748,179 and is cited herein in full for reference. The preferred temperature for the particle polymerization process ranges from about pA and the two preferred polymerization methods for the process that are (YY) 7001 m F) to about 0 59 m AAY ra

Ac gana and those that use a loop reactor run in a slurry phase; those that use a loop reactor in series; parallel 01; or combinations thereof. Among the stirred reactors of stirred reactors are examples of processes that take place in a stray phase, for example, but are not limited to continuous processes for 800760. Further examples described of tank alia conducted in a toroidal reactor or tank reactor where NIVEA of, slurry phase processes in US Patent No. 0 are mentioned in this statement in full for reference. In another embodiment the slurry process is carried out continuously in a loop reactor. The catalytic isobutane is injected or free powder in solution form; hanging; emulsion; slurry in isobutane fo sae uniformly to the loop reactor; Which is dry free flowing powder in a diluent growing polymer particles in turn with a slurry of a circle of growing polymeric particles 0 containing a monomer and a co-monomer. Optionally, isobutane can be added from isobutane and molecular weight control, as a molecular weight control, maintains hydrogen (kPa) to 4304 kPa (31700 kPa) on the reactor at pressures ranging from about psi' standard to 7175 psi' standard) and at a temperature in the range from 0 OY (F) depending on the density of 771 F to about Ee (about JUST about Veg because most of the reactor is loop wall Desired polymer The heat of reaction is removed through the ring wall and the slurry is left to exit through a doublejacketed pipe or continuously into a scald vessel in regulated intervals the reactor at regular intervals and into a nitrogen cleaning column A heated low-pressure rotary dryer flash vessel and all isobutane sequentially to remove the diluent from the nitrogen purgen column + monomer and unreacted co-monomers. The resulting free-flowing hydrocarbon powder is then formed for use in other applications. In an embodiment, the reactor used in the slurry-phase process and process is lbs of polymer per 1,000 (of the invention capable of producing more than 5097 kg/hr Gy lbs/hr); the most preferred over 50001 (hours); The best is over 77,768 kg/h vs

ANY

'From 40©; 0001 kg/hr (lb/hr). In the AT embodiment the slurry reactor used in the process of the invention produces in excess of 18,604 kg/hr (Yon pounds of polymer per hour); Preferably over 11460 kg/hr (lb/hr) to about 0 kg/hr (00001 lb/hr). In another embodiment the total pressure of the reactor in the slurry-phase sAD polymerization process (Gy) of the invention ranges from 7758 kPa (100 lb/in) to 7 kPa (Ar) lb/in; it is preferable 019 kPa (£04 lb/in' standard) to about 48717 kPa (Ve) lb/in' standard) and better than YEEA kPa (000 lb/in' standard) to about 87 ;; kPa To) lbs/in' standard); The concentration of ethylene in the process carried out in the Gay slurry phase of the invention in the liquid reaction medium ranges from about 1 to 701 by weight; preferably from about ? to about AY by weight; preferably from about Ye to of about 7” (oda and more preferably of about IY about 776 by weight. The preferred process of the invention lies in a process; preferably a slurry or gas phase process operated in the absence or essentially devoid of any scavengers, such as striethylaluminum and trimethylaluminum ctriisobutylaluminum tri-p-hexylaluminum ctri-n-hexylaluminum + 0 chloride JB ethyl aluminumehloride Overlaying; dibutyl zine and the like. This preferred process is described in PCT International Patent Bulletin Gg No. 96/088700 and US Patent No. ONY, YOY and is cited herein in full for reference. In a preferred embodiment of the invention; A slurry of JLB aluminum distearate in Cu mineral oil is introduced into the reactor; separately or with overlay AAV

1 the first and/or second metal and/or with an activator; of metallic compounds and/or steroids. More information about the use of additives can be obtained from the type of stearate additives in the US patent application with serial number aluminum stearate, American invention No. RA SURPRISE VAIN POR 01 11,771 / »; Deposited in February 1007 AD, as mentioned in this statement for reference, YA deposited in 1,091,176 + as a reference. And in embodiment; If the second metal compound and the metal containing compound of the catalyst system are introduced into the reactor sequentially; It is preferable to add V0 element from the group of the second metal compound and/or activate it first and add the metal compound that contains an element from

Gol and/or its activation 11 group - for catalytic compounds from about residence time “AT” and in embodiments © vo and about hours. preferably between about 71 hours to 71 hours about ' ethylene and in embodiment; The molar ratio of the co-monomer to ethylene ranges from about ethylene represents the amount of ethylene Cry where © , represents the amount of co-monomer ©. care A to about 1007 and better than about 10000 to about 1.800 (and other properties) for the polymer produced by melt index and the flux index may change in the polymerization system in the following manner: hydrogen concentration adjustment hydrogen Change the amount of the first catalyst in the polymerization system; and/or 1) change the amount of the second catalyst in the polymerization system; and/or )” to the polymerization process; and/or 8 hydrogen addition (Fv) change the amount of liquid and/or gas withdrawn and/or detergent from the process; and/or 8 and/or return extracted gas to recovered liquid Alter the amount and/or composition of an extracted liquid (0 and the said extracted gas or liquid is extracted from the polymer discharged from eld the process of the polymerization process; and/or in the polymerization process; and/or hydrogenation catalyst hydrogenation catalyst use (1 Yo

AAY

(V) change the polymerization temperature; and/or A) change the partial pressure of ethylene in the polymerization process; and/or 4) change the ratio of ethylene to hexene in the polymerization process; and/or 0) Changing the ratio of the activator to the transition metal in the context of the activation sequence, and the reactor hydrogen concentration ranges from about 001 to 500860 parts per million (ppm) parts per million, preferably from 00000 to 0000010 ppm; YOu best to 0,900 ppm; 00 to 180,860 ppm best; You to 170,000 ppm best; 400 to 1,000 ppm best Best from 000 to 15009 ppm; Best from 500 to 140 000 0 ppm; Best from © 0000 to 001 Best from 00 to Wer ppm; Preferable 700 to 1101 ppm, 800 to 0 ppm is best.The hydrogen concentration in the Lon Se reactor is proportional to the average molecular weight (M.) of the polymer.The catalyst and/or activator can be applied to; deposited on; come into contact with; vo incorporated in 0 adsorbed or absorbed into a carrier. The typical carrier may be any of the cporous solid carriers Lay, including microporous supports, and typical carriers include talc, inorganic oxides, silica Magnesium chloride ¢magnesium chloride alumina calumina silica-alumina ¢silica-alumina Polymeric supports Fie polymeric supports Y polyethylene (lil) polypropylene polystyrene polystyrene ¢ cross-linked polystyrene etc. Carrier preferably in finely divided form Carrier dehydrated Preferably Goa or WS before use Can be physically dehydrated physically or by calcining or by chemical conversion of each vo or part of the active hydroxyls.For more information on AAY

portable catalysts; See US Patent No. 4,808,971 describing a method for mounting metallocene catalyst systems. In addition; Ad Numerous other catalyst loading technologies are known Tua in tech. Methods for loading the metallic compound containing an element of the group Gay V0 of the invention are described in the US patent application pending with a serial number

M --8/A7,8 3/71..; filed VY May; 9991 AD, as mentioned in this statement for reference.

polymer according to the invention

The new polymers from the Gy process of the present invention can be used in a combination

wide range of products and end use applications. Preferably, new polymers include:

cpolyethylene, and it is also better to include di-polyethylene

© - Format produced in a single reactor. In addition to bimodal polymers; The production of monomodal or polymodal polymer is not outside the scope of present application.

It produces a metal compound containing a group 10 element when used

alone; Polymer having a high average molecular weight (Sha) of more than 100,000; preferably

be greater than Vos and preferably greater than 000090; Preferably more than 0,000,000

a and preferably more than (Yeeros and produces the second metallic compound; when used alone; low molecular weight polymer Nae) molecular weight less than Avene and preferably less than Veron and preferably less than een The best is less than 080050©; It is better that it is less than 500600, and it is better that it is less than 0000©, and it is better that it is less than 0080800; and more than 0080; It is better for it to be less than 700000 and more than 00001.).

a for polyolefins 0017016505 and in particular polyethylenes 5017607160856 produced by means of the present invention; Densities ranging from 84 to SAY g name gram/cubic centimeter (g/em'). Preferably, polyethylenes having densities from 4.40 to 0.975 g may be produced. /cm"; the best is from 200 to 1,970 g/cm"; Even better is from 0.0 to 1,900 g/cm. In some embodiments, the density is preferably from

AAY

. LS) measured according to the American Society for Testing Materials (ASTM D-1238) method, Envelope E at

0 0 19506 m) ranges from about 0.09 to 0.0001 decigram/minute (dg/min) or less. In a preferred embodiment; A polyolefin is a homopolymer or copolymer of ethylene and in a preferred embodiment for some applications; such as making films, pipes, molded articles, and the like; A magma index of 01 dg/min or less is preferred. and for some molded films and materials. Evidence preferred

© Magma of 1 dg/min or less. A polyethylene with a melt index of A between 0.01 and 10 dg/min is preferred.

In a preferred embodiment; The resulting polymer in this statement has a precise index (L, flow index WS) measured Gy for -88724-0-1238; at 00907 m) ranges from 1.1 to 10 dg/min; preferably 1.7 to V.0 dg/min; 01 dg/min or less is preferred; Preferably

1 dg/min or less; best from 0.5 to 0.7 dg/min or less; preferably 0.9 dg/min. 18 to 17 dg/min; And better than

In another embodiment; The Gay polymers of the invention have a magma flow index L/L; (MIR) melt flow index of 0 or greater, preferably 00 or greater; Preferably 001 or more and preferably 111 or more.

0 and in another embodiment the polymer I; (as measured by Gy to 1238 (ASTM circumferential at 00°C) (sometimes referred to as flow index) is ¥ dg/min or oil preferably 1.0 dg /min or oJ preferably 0.1 dg/min or less; #9 to Vo dg/min is best; 1.6 to 1.8 dg/min is best; 5 Bf; is Av or more, preferably 0 or more, preferably 001 or more, preferably 17© or more, and has one or more of the following:

m the following properties:

AAV to and 50. and Qais 01, preferably between Ve and Ye, preferably between Ar and 11, ranging between MYM, ) (A, molecular weight (,14 and ,24) as will be described Below in the examples part; or more; 750000 or more preferably 000001 or more preferably 1600001 Mw (b) or more; 5000060 preferably .,475 g/cm"; Preferably from ,448 to AY to 1.94(c) density ranging from 0 g/cm'; preferably from 450 g/cm' to 5470 g/cm' (as measured according to ¢(ASTM) 2839 > ppm or less than 5.0 aly residual metal content (d) residual metal content

VA ppm or less transition metal; preferably 7.0 transition metal; preferably ppm or less; 1.6 ppm or less transition metal; preferably 1 0.1 ppm or less transition metal”; preferably 0.9 transition metal; Preferably ppm VA Preferably of ppm or less of a metal chosen from the group 0.6 ppm or less of a metal preferably of or less than a metal chosen from the group Part per million or less of a metal, choose from 0.5, preferably of, choose from the group, preferably zirconium, or less than 7,0 zirconium, preferably of group 3, ppm 1.1 preferably ezirconium or less zirconium 0 preferably 1.0 parts per million or less zirconium zirconium or less zirconium for excitatory-coupled plasma optical emission spectroscopy Way Measure LS) zirconium where (ICPAES) Inductively Coupled Plasma Optical Emission Spectroscopy is conducted to decompose a commercially available sample where the sample is heated to standards 3 completely. The solvent includes acid organics decompose all organic compounds as a carrier sale if any carrier is present; To dissolve any AT and nitric acid (silica) To dissolve hydrofluoric acid carriers (such as hydrofluoric acid and/or; AAY

(e) a component with a high average molecular weight of 770 wt or greater; 0 wt. or greater is preferred; As measured by ¢ (SEC) size exclusion chromatography and in a particularly preferred embodiment the high molecular weight moiety is present in the range of 328 to 7970 by weight; And the best between Eo: and 770 wt. In a preferred embodiment the catalytic composition described above is used to produce polyethylene having a density of between 0.44 and 0.970 g/cm (as measured in accordance with 9 © 5724) 5 of 01.5 g/10 min or less In another embodiment the catalytic composition described above is used to produce polyethylene 00 having Li less than 01 and a density of about 94560 JPR A005 or Li less than 01 and a density of about 0.946 g/cm. " or less. In another embodiment; The polymer Why of this invention is formed into a tube by the methods known in the art. For pipe making applications; The Gy polymers of the invention Ly range from about IY to about 01 dg/min and preferably from about ? to about +dg/min. In another embodiment; The Gy tube of the invention meets the requirements of the international quality standards Ga of the International Standards Organization - (ISO) International Standards Organization and in the embodiment of “AT” the catalytic composition according to the present invention is used to make a polyethylene tube capable of withstanding for fifty years at least at an ambient temperature of 10°C » using water as an internal test medium + water or air as an outside environment (hydrostatic stress (framework) hoop as measured in accordance with 9080 (1so TR). In the HAT embodiment ¢ the jad gall has notch tensile strength in excess of 050. an hour at 7.0 megapascal “(MPa) megapascal and preferably more than 00 hours at ¥ 0 MPa and preferably ve more than 01 hours at 3.0 MPa as measured by Gy For (ASTM F1473 AAY

In another embodiment; The Gay catalytic composition of the present invention is used to make a polyethylene pipe having an expected value of .71 5-4 for a pipe length of 11.0 millimeter (mm) less than -©m; Preferably less than a Vom, preferably less than 40 m (according to ASTM (ISO 015 89). In another embodiment, the polymer has an extrusion rate of more than about 1 4 kg h/cm h/cm. /1 VV lbs/hour/inch (Ibs/hour/inch of die circumference preferably more than about YY kg/hr/cm Yo lbs/hr/in) of The circumference of the mold is preferably more than about yo kg/hr/cm YY (lbs/hr/in) than the circumference of the mold.

1 The GE polyolefins of the invention can be made into films; molded materials (including pipes); Csheets: Coating for wires and cables, and the like. The films may be formed by any conventional technique known in the technique including cextrusion, co-extrusion, blowing fii) lamination and casting 8. The film may be obtained by the flat film process or

| In a unilateral orientation, which can be followed by a flat film or tubular process vo mutually perpendicular, or in two mutually perpendicular directions, the axis of the film to similar or different degrees. Orientation may be in the same plane at a level of 5 degrees in both directions, or in different degrees. A particularly preferred method for shaping polymers is extrusion or co-extrusion films on a blown film line or

.blown or cast film line Casting y.

In the OAT embodiment the polymer according to the invention is formed into a film by methods known in

The technique. For membrane applications; The polymers according to the invention have,,a range from

about AY about 50 dg/min; Preferably from about? to about Yo

decigrams per minute Even better, from about 7 to about 10 dg/min; Even better is AAY

From about © to Ve Ja dg/min and even better from about * to about Vo dg/min. And in another embodiment; The polymer has a tear in the AY direction) of the MD tear of a film thickness of 8 mil (VY mil micrometer (m)) ranging from about © g/mL to (defo Yo) preferably between about VO g/ml and 75 g/ml; the best is about Yo g/ml You g/ml The resulting films also contain additives such as eslip and cantiblocks antioxidants pigments pigments Fillers Antifog Cantifog UV stabilizers Electrostatic agents Jal so cantistats Polymer processing aids Oll dyes surfactants Surfactants clubricants lubricants ¢neutralizers ve Preferred additives include silicon dioxide nucleating agents and nucleating agents titanium dioxide synthetic silica silicon dioxide “calcium carbonate” cpolydimethylsiloxane dimethylsiloxane “calcium stearate” metal stearate 85 lignans calcium stearate

yo zine stearate tale 3850 diatomaceous earth wax wax carbon black flame retarding additives low molecular weight resins resins, chydrocarbon resins, glass beads, and the like. Additives with known effective amounts (Bale Tas) may be present in the technology; Se ranges from 705009 wt. to 701 wt.

, and in another embodiment; The polymer according to the invention is formed in the form of a molded material by methods known in the art; For example; By blow molding cblow molding blow molding and injection molding 0©165: -60000g. For molded material applications; The Gy polymers of the invention have: A ranging from about 0 0 dg/min to about 0 0 dg/min and preferably from about YO dg/min to about ©; deg/min.

AAY

In another embodiment the polymers obtained according to the invention are: including those described above; Ash content of 880 is less than 001 ppm sala and preferably less than Yo ppm; It is also better if it is less than on ppm. In another embodiment, the ash contains trace amounts, fas, of titanium as measured by Coupled Plasma/Atomic Emission Spectroscopy (ICPAES) as is well known in the technique. dg is another embodiment; The ly polymers of the invention contain a nitrogen-containing ligand that can be detected by High Resolution Mass Spectroscopy (HRMS) as known by us in the technique. 1 examples to better understand the present invention including its representative advantages; Aha) introduces the following. Measurement, 14 My, by gel permeation chromatography (GPC) using a gel-permeation chromatography instrument of Waters type at 0150 m equipped with differential refraction index detectors The GPC columns were calibrated using a series of molecular weight standards and the molecular weights were calculated using the Mark Houwink coefficients for the respective polymer. According to ASTM 1505 © Magma Index Gag (MI) I, for (ASTM D-1238) measured envelope a at 190 m. Gy I, for (ASTM D-1238) measured envelope og at 198 M. The Melt Index Ratio (MIR) is represented by a ratio of , O to I Cand, the weight ratio of the copolymer using the nuclear magnetic resonance (Yo) (NMR) Nuclear Magnetic Resonance by proton .proton AAY

The sagittal dart impact was measured according to 1709 ASTM D, and the Elmendorf tear was measured towards the machine and in the transverse direction. MD and TD Elmendorf Tear according to 1922 © ASTM. The cutting coefficient was measured 71 secant modulus in the direction of the machine and the transverse direction According to ASTM D 882 °, tensile strength and ultimate tensile strength were measured in the direction of the machine and in the transverse direction. According to ASTM D882, elongation and ultimate elongation were measured in the direction of the machine and in the transverse direction. According to ASTM D 412 and measured coefficient in machine direction and transverse direction MD and TD Modulus according to ASTM 882-91. Gb g haze was measured for 1003-95 (ASTM Envelope A) and measured Gloss £0 Ga 5 45 gloss to 2457 ASTM D Jiey BUR Swelling ratio up ratio Matt vo 1 denotes cpounds per hour and “'mPPH” denotes to millilbounds per hour, and “no” refers to the number of parts per million by weight. on a huge bundle; It is also represented by the form (VI) ve and can be prepared by performing the following general reactions: (1( Zr NEt), + ndH——IndZr(Et,); + 3 (Y) IndZr(NEt,), + 3(CHs); CCOH———>ndZr[0,CC(CHs)}s + Et,NH where Ind is indenyl and Et is .ethyl ligand preparation [(2,4,6 -MesCoH,)NHCH;CH, |, NH (ligand ?) AAY

A two-liter one-armed Schlenk flask shipped with a magnetic stir bar and 77.490 g YY V + mol of diethylenetriamine, 0.81 g (°£0 mol) of 1”-<bromoacetylene 0.1 1 2-bromomesitylene g (0.1 mmol) of tri(dibenzylideneacetone) A. palladium 1 071 (dibenzylideneacetone)dipalladium g TLE (mmol) of 7:7-di(Diphenylphosphino)-010”-dinaphthyl-racemic-2,2”-bis(diphenylphosphino) - cas; BINAP) 1,1'binaphthyl (( 10,010 g (147 mol) of sodium tertbutoxide 800 mL of toluene in a dry nitrogen atmosphere JA of oxygen oxygen and the reaction mixture was stirred and heated to ¾ 10 M. After dela YA the reaction was completed, as determined by proton NMR spectroscopy All remaining treatments could be carried out in air and all solvent removed in vacuum The residues were dissolved in one liter of diethyl ether Jul, and the ether was washed with water three times at an amount of 750 ml (ml) milliliter each time, then with a saturated aqueous solution of 088 000 gm of NaCl (NaCl) ml and dried over Yogm of Jo sulfate Magnesium sulfate The removal of ether resulted in vacuum 1.1 gm of red oil dried at 07 m for VY hours in a vacuum (production rate = 797). 'H rang m (WL6) delta YVR (£0) LAY (q wide; VAT (1 nv) 14 s 8) 7.77 (V 1.11 (OY 1) 18 (F bold.” 1. Preparation of catalyst A © Preparation of a solution of catalyst A with a concentration of 71.5 wt. in toluene Note: All procedures below were carried out in a glove box 1 - Weighed 001 g of purified toluene added to a 1 liter Erlenmeyer flask fitted with a Teflon-coated stirrer 7-V, YA added 1 g of tetrabenzyl zirconium zirconium ANY oY for © minutes All the solids dissolved in the li agitator The solution was placed on a stirrer -* the solution. g (00 mg) additional toluene 8.7 00 added —o

to flip for 0 minutes. No solids were left in the solution.

1- The catalyst solution was poured into a whitey sample cylinder with a capacity of one liter, which was disinfected, clean and labeled. It was removed from the glove box and placed in a holding area for operations. An alternative method for the preparation of compound 1 NCH,CH,]; NH} Zr(CH Ph), (Matt: 2,4,64»:0)])

Vv an 8958 mL round bottom flask was loaded with a magnetic stir bar with 41,774 g (91.07 mmol) of tetrabenzyl zirconium (obtained from Boulder Scientific) and 00 ml of toluene in a dry nitrogen atmosphere through oxygen. Added “a gm (47.07 mmol) of the above solid ligand 1 with stirring for a minute

one (where the desired compound precipitates). The volume of the slurry was reduced to 100 ml and 0 ml of pentane was added with stirring. 1871 grams of solid yellow-orange product were collected by filtration and dried in vacuum. (production rate = 7860).

3 rang m (CD) delta LAY=V,YY (p (VY 40 in FAY Ye) VFA (Y y. )=( i.e. (v.1 7,15 (p) 10 Y,ev (3 1) Cra (V 1) Gla (V D) Cra AT (Ya) (P” AY Preparation of the catalyst b Prepare a solution of the catalyst with a concentration of 71 by weight in hexane hexane All procedures were carried out in a glove box ANY or 1 liter purifier supplied to a hexane Erlenmeyer flask 1 liter hexane-1 teflon transport with a triplex teflon-coated stir bar Indenyl zirconium pivalate dried powder A gram of dried powder LAY was added -“ indenyl zirconium tris pivalate Melted Cua for 11 minutes and stirred for 11 minutes magnetic agitator Putting the solution on a magnetic stirrer -* All materials The solid in the solution. ;- Pour the solution into a whitey sample cylinder with a capacity of one liter, which is clean and disinfected, and a card is placed on it. It is removed from the glove box and placed in a preservation area until it is used in the process. 1 Comparison example. 1: In a gas reactor, ethylene-hexene, then producing a copolymer of ethylene-hexene, measuring 8.1 cm, pilot plant scale gas phase reactor, on the scale of an experimental industrial unit.

Jl Sl ae ¥, in) operating at 65 m and at a total reactor pressure of V £ (standard Jia water cooled heat exchanger). 18.1 lbs per to the reactor at a rate of about ethylene and ethylene feed -2 kg/hr (7 lb YY) to the reactor at a rate of about hexene and dela mg/hr (5 mM) Y,Y0 to the reactor at a rate of hydrogen per hour) and hydrogen fed make-up gas to the reactor as nitrogen (lb/hr) and fed nitrogen (lb/hr). The rate of A was at a rate of It ranged from about 7.76 to 3.6 kg/hr (0 to 0 lb/hr (717) kg/hr (about 1.1) production rate Y. at a rate of about 56 m recycle gas flow containing a plenum lb/hr recycled gas flow (and fullness is a means used to create a particle-poor zone of 0 (kg/hr) in a gas phase fluidized bed reactor; as described In detail in the particle lean zone patent US Patent No. 5,147,777 where it is mentioned in this statement for reference. cm 001 I opened it aaa tapered catalyst injection nozzle and put a tapered catalyst injection nozzle

AAY of

ZN inches) in the fullness in which the gas flows. A solution of catalyst A concentration (EY) +, aluminum containing aluminum (MMAO-3A) was mixed with a co-catalyst (toluene by weight in toluene by weight) in a single line before passing through the injection nozzle to the fluidized bed. and 71 at a concentration of cheptane modified in heptane methylalumoxane is MMAO-3A methylalumoxane with the trade name Akzo Chemicals, Inc. M - commercially available from Akzo Chemicals Inc. to the catalyst so that The ratio was MMAO and the ratio of Modified Methylalumoxane type 3A was also adjusted to isopentane and isopentane nitrogen and nitrogen feed Vifer ZnAl molarity of constant average particle size Injection nozzle as needed to maintain average particle size dg/min and the density +, YA nominal amounted to I. A monomodal polymer with a zirconium value of 4.40 g cm was obtained. According to the remaining amount of zirconium, it was 7 ppm by weight. On the basis of the reactor mass balance Comparison example? A copolymer of ethylene-hexene was produced in a gas-phase reactor with a scale of Lelia Auld 70.7 cm (VE inch) Operating at a he and os a total reactor pressure of 7.7 MPa (4 YY psi” standard) with a water-cooled heat exchanger. Ethylene was fed into the reactor at a rate of about 19.8 kg/in. TV hour (pounds per hour); Hexene was fed into the reactor at a rate of about A (+ kg/hr (+ pounds per hour) and hydrogen was fed into the reactor at a rate of about 9.4 mg/hr (VY) millilbs/hr). Feed ethylene to maintain a partial x pressure of ethylene in the reactor of 0.7 MPa (VA (psi). The production rate was about VY, Yo (kg/hr (Yo) pound/inch). The reactor was supplied with a filling containing a recycled gaseous effluent at a rate of approximately 474 kg/hr (Vor (lb/hr). (Fulfillment is a method used to create a particle-poor region in a fluidized bed gas phase reactor.) A tapered catalyst injection nozzle with an opening size of 004 cm (+ 000 inches) is placed in the filling of the © into which the gas flows. A solution of the catalyst with a concentration of 71 by weight in 6:002 hexane was mixed with AAY.

Hexene flows at a rate of 1509 kg/hr (7© lb/hr) in a stainless steel tube of length EA + cm (¥ [1 inch]) for approximately 0 min. The mixture of catalyst B and hexene was mixed with a co-catalyst (MMAO-3A) containing aluminum with a concentration of 71 by weight) in one line for about 560 minutes. In addition to the solution, isopentane and nitrogen 0 were added to control particle size 0 and system J was passed through the injection nozzle into the fluidized bed. The ratio of MMAO to catalyst was adjusted so that the molar ratio was .:001 21 and a bimodal polymer with a flux index of VAY g/10 min was obtained. The density was 9774 g / cm. The remaining amount of zirconium, which was nV ppm by weight, was calculated on the basis of the cyclic equilibrium in the reactor. The analysis of 1 size exclusion chromatography (SEC) and descaling was completed. Using four Fluorine distributions, the results are shown in Table 1. Example + A copolymer of ethylene-hexene was produced in a gas-phase reactor with an experimental industrial unit scale of TOT cm VE (inch) operating at a Ae and at a total reactor pressure of 7.7 MPa (+TY psi' standard) equipped with a Se water heat exchanger. Ethylene was fed into the reactor at a rate of about YE kg/h oT (pounds per hour); hexene was fed into the reactor at a rate of approximately “YY kg/hr (7 lb/hr) and hydrogen was fed into the reactor at a rate of © of 0.1 mg/hr ( 9 mm lb/hr.) and feed ethylene to maintain a partial pressure of ethylene in the reactor of 0.97 MPa (7701 lb/in). The production rate was about 11.75 kg/hour (Yo) pound/hour). Fill the reactor with a recycled gaseous effluent at a rate of about 7?; kg/hr (990 lb/hr). (Fulfillment is a method used to create a particle-poor region in a fluidized bed gas phase reactor.) - A tapered catalyst injection nozzle with a bore size of +VY cm (+100 inches) was placed in a fullness of AAY

01

Gas flows into it. A solution of the catalyst with a concentration of 71 by weight was mixed in hexane = & hexene, flowing at a rate of 1.09 kg/hour (17 lb/hour) in a stainless steel tube of length 1.448. cm (VY inches) for about 11 minutes. The mixture of B and hexene catalyst was mixed with a co-catalyst (MMAO-3A) containing aluminum at a concentration of 1 0 by weight) in one line for about 70-71 minutes. And in a steel tube no faa for separate marking; A solution of catalyst A 71 wt. in toluene was activated using a co-catalyst (MMAO-3A) containing 71 wt. aluminum for about 0-0.0 min. The two activated solutions were mixed separately in a line for a single process of approx.; minutes. The amount of catalyst A was about 46-7489 in moles of the total nutrient solution. 6 In addition to the solution; Isopentane and nitrogen were added to control particle size. The aggregate system is passed through the injection nozzle into the fluidized bed. The ratio of MMAO to catalyst was adjusted so that the molar ratio of 2:81 was 1:700. A bimodal polymer was produced with a melt index of 0.040 g/10 min and a flow index of 7.58 g/10 min. The density was 717 ,; g/cm'. The remaining zirconium was calculated as 1.1 ppm by weight on the basis of the mass balance in the reactor. SEC analysis and deconvolution completed

Using the AY distributions from the fluorescent distributions, the results are shown in Table 1.

example; Then production of a copolymer of ethylene-hexene in a gas-phase reactor at the scale of an experimental industrial unit measuring 08.7” VE cm (inch) operating at aie ga Ao + a total reactor pressure of 7.7 MPa. YY (psi' standard) with water-cooled heat exchanger. Ethylene was fed into the reactor at a rate of about 17.17 kg/hr (50 lb/hr) and hexene was fed into the reactor at a rate of about TY kg/hr + .V lbs. per hour) and hydrogen was fed to the reactor at a rate of 58 mg/hr (11 millilb/hr). Feed ethylene to maintain an Er pressure of ethylene in the reactor of 0.87 MPa (771 lbs/in). AAY ov production rate was approximately YA) 11 psi A filling containing a recycled gaseous effluent at a rate of about 4717 kg/hr (AY) was provided to the reactor (lb/hr). fa a tapered catalyst with an orifice of 0.14 cm (4,000 in.) in fullness in which the gas flows. oe and a solution of catalyst B of concentration ZY mixed by weight in hexane with hexene flowing at a rate of 109 kg /17 lb/hr in a No. 144 A ghana cm VT steel tube for approximately 0 min. Mix the catalyst mixture B and hexene with a co-catalyst (MMAO-3A) containing aluminum at a concentration of 71 wt.) in one line for about YoY. min. and in a separate activation stainless steel tube; a solution of catalyst A of ZY by weight in toluene was activated using a cocatalyst (00180 -38; contains aluminum with a concentration of 71 by weight) for approximately 00-50 minutes. The two activated solutions were mixed separately in a line for a single process of approx.; minutes. The amount of catalyst A ranged from about 748-660 in mol of the total nutrient solution. In addition to the solution; Isopentane and nitrogen were added to control particle size. The aggregate system is passed through the injection nozzle into the fluidized bed. The ratio of MMAO to catalyst was adjusted so that the ratio (A gd) was 2:41 5 . A bimodal polymer was produced with a melt index of 1054 g/10 min and a flow index of 4 g/10 min. The density was 1.44 g/cm'.” The remaining zirconium was calculated as 11 ppm by weight based on the mass balance in the reactor. SEC analysis and deconvolution were completed using AY distributions from Fluorescent distributions show the results

Ideal In -© Example #5 a copolymer of ethylene-hexene was produced in a 78.7 cm VE pilot unit scale gas phase reactor operated at 85 °C and reactor pressure JS 7.7 MPa (TY 0 psi) with vo ue heat exchanger with water. ethylene was fed to the reactor at a rate of about 77.7 kg/hr (AAV oA to the reactor at a rate of about hexene (lb/hr); Hexane (1+) was fed into the reactor at a rate of hydrogen (kg/hr (0.48 lb/hr) and hydrogen was fed “YY to maintain ethylene pressure at 1 mmlb/hr). and feed ethylene (1 ¥) at 0.4 mg/hr (lb/in). and (YY +) 1.0 MPa into the reactor was ethylene partial ethylene (lb/hr). and supplied A full reactor has a production rate of approximately 15.7 kg/hr (YE) 0 recycled gaseous reflux at a rate of 477 kg/hr (410 lb/hr). Fluidized Bed Gas Phase Reactor) and placed 1.14 cm (000+ inch) in fullness to which a 1.14 orifice size tapered catalytic injection nozzle flows with wt hexane in 71 hexane gas. of catalyst B at a concentration of lbs/hr) in a 17 stainless steel tube (109 kg/hr flowing at a rate of 0 hexene with 0 hexene min. and mixing the mixture of catalyst B and 0 hexane) for approximately VY) cm + EA by weight) in one line 71 containing aluminum at a concentration of (MMAO-3A) co-catalyst min. In a separate activation stainless steel tube; active solution of catalyst 70-71 for about using a cocatalyst (20480-3/8; containing toluene by weight in toluene 1/a min. and mixing the two activated solutions 50-00 wt) to about 71 wt. 1 each separately in line for a single operation of approx. minutes. The amount of catalyst A ranged from about 6-746_ in moles of the total nutrient solution. In addition to the solution; Isopentane was added through the J nozzle to control particle size. The system passed nitrogen and isopentane to the catalyst so that the molar ratio of MMAO injected into the fluidized bed. The proportion of particles and index 01 / mg + VY was adjusted, and a bimodal polymer with a magma index of .0:7001 71 Y. g / cm was obtained. And according to the remaining amount of 19448 minutes. The density was 01/mg, 17.7, and the flux was ppm by weight, based on the mass balance of 1.9 zirconium. Distributions from AY fluorescent distributions and deconvolution using SEC. reactor. Analysis completed

I The results are shown in table ro

AAV oq + example in a gaseous ethylene-hexene reactor and then producing a copolymer of ethylene-hexene m and at AS in (operating at VE) phase in an experimental industrial unit scale measuring 78.7 cm psi' standard) supplied with heat exchanger YY +) MPa YY of the reactor of IS pressure into the reactor at a rate of about 1.7 kg/h water-cooled ethylene. feed ethylene (0 lbs. per hour); Hexane 066606 was fed to the reactor at a rate of about 1) to the reactor at a rate of hydrogen per pound per hour) and fed hydrogen +A (kg/hr + to maintain a partial pressure of ethylene mmlb/hr). Ethylene was fed 1” (mg/hr 4 lb/in). The YY rate was 1.07 MPa in the reactor of ethylene per lb/hr). The reactor was filled to capacity containing Flow TE) kg/hr 15.7 Production approximately 0 lb/hr (and filling 0101) Recycled gaseous at a rate of approximately £90 kg/hr A means used to form a particulate-poor zone in a reactor Fluidized-bed gaseous phase). 1.14 cm (+100 in) in fullness of a tapered catalyst whose orifice size (fa) was placed in a nozzle with hexane by weight in hexane 71 into which the gas flowed. A solution of catalyst b concentration lbs/hr) in a 17 stainless steel tube (109 kg/hr flow rate hexene-hexene min. and mix catalyst b and hexane VO inch) for approx. (VY) cm + EA length by weight) in 71 at a concentration of aluminum containing aluminum MMAO-3A) with a cocatalyst by weight in 71 minutes. A solution of catalyst A of concentration 15 was added 01- One line of about in sprayed activator B and left for about 0 minutes before spraying it (liad) into a solution of toluene in the reactor. The amount of catalyst A ranged from about 45-668/mol of the total nutrient solution © to control the volume of nitrogen and isopentane as well as the solution; Isopentane was added

MMAO particles. The aggregate system is passed through the injection nozzle into the fluidized bed. The ratio of the resulting dimeric polymer of .010:0 2 to the catalyst was adjusted, as the final molar ratio was minutes. The density was 01 mg / TAY minutes, and the flow index was 0 g / NTT.

AAY

. in million by weight based on the mass balance in the reactor. The SEC analysis and deconvolution were completed using 1-8 of the fluorescent distributions and the results are shown in Table 1. Example 1

A copolymer of ethylene-hexene was produced in a gas reactor.

0 phase on a 35.7 cm VE (in) experimental unit scale operating at a Ao and a total reactor pressure of 7.4 MPa (+TO psi) with water-cooled heat exchanger Ethylene was fed to the reactor at a rate of about 19.1 kg/h

(7; pounds per hour); Hexene was fed into the reactor at a rate of approx

¥1, + kg/hr (8 lb/hr) and hydrogen was fed to the reactor at a rate of

6 4 mg/hr (VY lb/hr). Ethylene was fed to maintain a partial pressure of ethylene in the reactor of 0.07 MPa (YY) lb/in). The production rate was about 14.4 kg/hr (YY) lb/ hour).

recycled gaseous at a rate of 905 (0 Ye) lbs/hr). (Fulfillment is a method used to create a particle-poor region in a fluidized bed gas phase reactor.) A catalytic injection nozzle was placed

- A taper whose opening is 14 cm (000+ inches) in fullness into which the gas flows. A solution of catalyst with a concentration of 70.75 by weight in hexane was mixed with hexene flowing at a rate of 0.06 kg/h (+ lb/hr) in a stainless steel tube of length tA cm.

(MMAO-34) with hexene co-catalyst (in). And mixing the mixture of catalyst B and hexane (1 Y/Y min. 15 by weight) in one line for about ZN of aluminum concentration

x. A solution of catalyst A with a concentration of 75.5 by weight in toluene was added to a solution of catalyst B activator and left for about 11 minutes before being sprayed into the reactor. The amount of catalyst A ranged from about 5-7970 in moles of the total nutrient solution. In addition to the solution; Isopentane and nitrogen were added to control particle size. The system passed JK through its mouth

Injection into the fluidized bed. The ratio of MMAO to catalyst was adjusted so that it reached the threaded ratio

we final results of .000 Zeal and yielded a bimodal polymer with a flux index of 0.00 g/10 min.

AAY

and a flow guide of 7g/10min. The density was 10.5001 g/cm. The remaining zirconium was calculated at 1.76 parts per million by weight on the basis of the mass balance in the reactor. SEC analysis and deconvolution were completed using 8-17 fluorescent distributions and the results are shown in Table []. ° table I lg ——_—_— JE comparator 1 comparator 1 and $ ° 3 7 cc cc cc a —_ Ip) (dg/min) ed not available now Kyla YAN YY, NFC L/L, - - aa 1211 ym 6 Ip (dg/min) no flow ete am “YY ve 08 “ego vay” SEC trial data Aves Mn 77 No 01 01 Alal 013 Ya Lam Mw M 7774 34 YITAYE YAMIM YAYSTY YIIIFA Mn/Mw M 84 9 and YY.

Yo,¢ Ys, Mn (Calculated) - ~ 010 Vevy 017 Vito Mw (Calculated) . - - YALAYE 00 YEAYVS YOAYAY ¥rivey 7 (calculated) - - £688 YE, EA 117 for 7 LMW Mn (calculated) - kha 7761 8 5771 tel m LMW Mw (calculated) - 117/7 77 7 0m 9*4 10 LMW Mw/Mn (Calculated) - vot £,¢Y a YAY Y,AV HMW Mn (Calculated) 7214 - 71 mm 1114 AAYY £ AC £1) YYIYel HMW Mw (calculated) Eovory - 14 kW mil 770 HMW Mw/Mn (calculated) 0.03 - 8.1 $0 1.AA ov 0 ¢8,£ HMW (SPLIT / TOTAL) Vee Zero No 8 847 ¥ oY, AAY

> Reaction conditions 2a Reactor temperature (2°) Ao Ao Ao Ao As As Ao Pressure 20 [asf Ja; Cy] vapor R V,0/YY.

V,0%/YY.

V,0/YY.

V,07/YY.

VOY/YYe MPa VOY/YYe Molecular Ratio of L and 11/Minyl Me Glben (eee) SAN eet eed ey Molecular Ratio of CoC h. They say no “IN” reo vey Residence time (hour) A except , 8 A La La 8 Mole ratio of LMW/HMW - - + vinegar Prepare 11" AR Molecular percentage of catalyst A TA Ey gy 1 3 - Yoo Zr (ppm) in the lab - - A 1 AY oA yy Zr (ppm) at feed stream of < 4 Ah 715 - yar L mean VAS VY VY 7 YE - Vr Molecular Ratio of YY.

Yarr. - fee Zr/AL no catalyst activity b (g polyethylene/mm - - 1410 FYYAA YAVOE yYoro 07 mol of catalyst - h) catalyst activity a (g polyethylene/mm yeood - p every 77 mg Yiv.y moles of catalyst-hour) and example provides comparison 1 and 7 of experimental data on how a two-component catalyst system performs

single. Show two examples? And the; The effect of temperature on essentially identical reaction conditions

and catalytic feeding system. It is noted that at an elevated temperature; dad 100/148 is low.;

0 as the magma flow rate value. Examples © and 1 compare the effect of the activation regime for essentially identical reaction conditions and the catalyst feed system. It is noted that in Example 6 the overall efficiency of the catalyst was good. However, the amount of the substance with high molecular weight was low. Examples + and illustrate the ability to adjust the amount of a higher molecular weight substance produced in the reaction conditions

iy is basically symmetrical. In example (7); A larger amount of catalyst A was fed, so more material with a higher molecular weight (Mw) was produced

Example A 154 kg YO (lb) of polyethylene produced in example ¢ 0 above (indicated as polymer A) was synthesized using a Wimmer-Flederer ZSK-30 twin screw extruder Wemer-Fleiderer ZSK-30 twin screw extruder with 0001 ppm Erganox (trademark) V+ VT 1076 7" teardrop 1 and 1000 ppm Irgafos™ 1068 commercial idle V+ TA at a melt temperature of YY.C, and then shaped into pellets, then pellets were formed by blowing to obtain a film with a thickness of VF micrometers (100 ml) in a blown film extrusion line from Alpine type Alpine blown film extrusion line and the extrusion conditions were as follows: A triplex mold of 0 mm diameter was used ¢die-160 mm triplex die gap of diameter cake V,0 mold temperature of 405 m ; and the lay flat width Jassie was 1177 cm (£A inches); target magma temperature of 1077°C (004°F); extrusion rates of 144 kg/hr (701 lb/hr); 151 kgh (7lb/h) and 5107 kgh (0 lb/hr). ESCORENE™ HD 7755.10 (a conventional chain reaction product supplied by Exxon Chemical Company, Houston, Texas) was used under the same conditions as in the comparison examples. The films were AS conditioned at a YY and a humidity of 6 7/5 ©a for 56 hours. The data are recorded in Table A.

AAY

+ Schedule A ——— Polymer A 7755.10 HD Polymer A 7755.10 HD Polymer A 7755.10 HD EL AA AA TL —_ Rate lb/hr (kg/hr) (Y+9) £1 . (Yay) 471 (Yr) 471 (veg) vy (hee) 1 116 Measuring diaphragm 4 μL (IY) denotes VY 1 μL H4 μL NY w 4 ml / 1 km ml 0/ µm µm µm µm µm µm Density gm “qt a0. +444 EIN anf resting on the sagittal ram at a distance of 16 cm Yoo gm 8 gm 1 gm 8?? g Not mentioned Not mentioned 1 (inch) for the day of sagittal impact at a distance of 1 cm YOO g Yo A g 0 g 4 g VN g 0 g (ay 77) for Y days. g/µm) tear in the transverse direction (Y.18) A ASIIREE (77) At (v7) vv (£0) 0 (YAY) av g/mL (g/µm) secant 79 in the A direction Babila 6 as 11 + lakh psi" (MPa) (11) (0177) (17767) (1) (YAY) 1777 transversal 71 secant; df psi” (MPa) (Yo) (11) ( (275) 1177 (r¢10) (YYVvY) Ultimate Tensile Strength in Machine Direction A 1110 101/4 774" 14" mf dl (MPa) (+) (+) (AY) (19) (49) (4+) Ultimate tensile strength in direction VY EAY YAVYY YYYVA Y.VAS “1714 trans lbs” (v9) (A) (Ae) 75 (At) (4Y) (MPa) Maximum elongation percentage yoy Yan Ye Yay YAO 145 Maximum elongation percentage ray TY m ve. yyy Lal Blur percentage 04.1 oV,A TE, 1 84 4 Gloss 45 1 RMA 6 P 14 8" ASMS L Escorin HD7755.10 is a polyethylene polymer supplied by ° Exxon Chemical Company; city of houston; Texas ¢ has a Ly of 0 ov, magma index ratio - um 0 v um hm b wa with a rate of Mw ¢YYo in volume (YA v0 o density 0 q0 L daa g /cm ¢ is produced using a -dual reactor system ANY

+ Example 9 Several drums of granular samples (produced following the polymerization procedure described above) with a catalyst molar ratio (catalyst A/catalyst B) of YF were mixed by stirring with 0 ppm of Irganox (trademark) Slrgafos™ 1076 01776™ and 0001 0 ppm of Ergafos (trademark) 0001 Slrgafos™ 1068 00364 ppm calcium stearate and then pelleted 10 tumble-mixed granular resin using a Prodex forming line of 8 cm (0.0 inch) at (Ee) ATE, and the pellets prepared in this way were extruded in the form of a film using a 50 mm long Alpine blown film line Equipped with a single-riveted slotting tool of length (Cal) mm (L/D ratio: 18) and an annular die of 0 mm in diameter with a die gap of 1 mm in diameter. The slitting conditions were as follows: mold temperature of Tf m (400"F); production rate of £1 Gel ufo aS 01 (lb/hr). The profile diagram for a typical temperature range was as follows: Yee] Seg] for Cam in Lint YA) Sf SN F [GE Fff 01 K 01 K] for 1st barrel/2nd barrel/block adapter bottom bottom adapter /vertical adapter 3all/vertical adapter ¢ bottom of die 016/die middle 3—all/die middle ¢ top of die top Sample pellets were extruded to produce a YO µm film sample (da) at a line speed of £A cm/sec AY dae ((fom) feet per minute + 11 µm diaphragm (de v,0) ) at a line speed of 94 cm/sec (VAL feet per minute) at a blowing ratio (BUR) of 0.4. In both cases, the BLS bubbles showed excellent results and had the shape of a wine glass. The frost line hight (FLH) frost line hight of a gaily formed bubble was maintained at 4 cm (Ras TT) and 7010 cm (£0 in), respectively for a YO μm membrane. 01 (yo ml) and .1* μm (5 mm in). The head pressure values were AAY

1 users of the extrusion process slightly higher than those values used for motor load and motor load (Exxon conventional chain reaction product HD7755.10 Escorin (trademark) Alla call Texas) at the same conditions Mt Belvue Chemical Company in Mt. T Bellevue and the properties of the resulting film are listed in Table B. All membrane samples were conditioned at 77 °C; and proportion

VY,0 hours. The sagittal impact resistance of a membrane measuring 506 was 750 for a period of + gm; It exceeded that of Escaurin (trademark) FAL µm (4.0 ml) g.YY which reached HD 7755.10 Table B Escaurin (trademark) 7755 _ Polymer B occupies oA (01gqd/mg) 1,

Vey 1 (01 μg/mg) m 1 “7 L/L, density (g/cm”) 7 a

Veo Viet Yield (lbs/hr) (£v) (£v) (kg/hr) A About Adon co JE Yield using (lbs/hr/in of mould)

VAIN VY oo PRESSURE HEIGHT lbs/in' (MPa) 1 ..( 1 0 Engine Load (A) 1 1 BUR £ 4 2 5 (in) (cm) FLH (01) (91.5) (+) (3),€) Fusion fraction did not occur did not occur did not occur Bubble stability Good Good Good

AAY

Tv

YAS 9 Tension Speed (ft/min) (m/t) 9 Moha (+9) (+2) (+3) (+2) '0 1 a 1 Diaphragm Gauge (ml) (µm) ) 1.*( (Ye) (1Y.2) (Ye) How Much Yd. YY. You. (a2) Sagittal Impact Strength Tensile Strength (lbs/in') (MPa) 1106 A Lm Ato AY in the direction of (v4) the (vA) (oA) ov, VYY. Veto va. in the transverse direction (05) (©) (VY) (°°) ) 7) Elongation Ye, 0 79 Yo. AY in the direction of 1 oA. va. ov. in the transverse direction Mendorf tear (g/mL) (g/µm) B Ye YY Yo in the direction of the machine (V7) (+49 ) (+A) (+44) 2 Yio VY VEY transverse (14°) (nV) (77) (0) Modulus (psi") (MPa)

Yoyo, 18 in instrument direction ella 00 A (arr) (2+V) (247) (Av) H 6 V VET in trans direction (+VA) (V0) (Vy1o) (Ov) 01 Example 2 Following the procedure for Example 9; Mixed several cylinders of granular (polymer) samples

VEY obtained by following the polymerization procedure described above, with a molar ratio of catalyst A to catalyst B of

AAV

TA

and polymer D obtained following the polymerization procedure described above with a molar ratio of catalyst A to catalyst B

Ve ppm of Er Ganox (trademark) 0 by stirring with (Y 3) reached ppm YO uu calcium stearate ppm of calcium stearate 1 then formed in the form of pellets and extruded by the method described 0164 by Ergavos (trademark) for 460 h. 7500 in Example 4. All films were conditioned at 77°C and a humidity of 05 µm (+0 mL) of both polymers of 17.5 and showed a resistance Sagittarius hit the measuring membrane

HD 7755.1 exceeded that of Escorin (trademark) Cum cae FAL and d by C z g. The results are reported in Table YY. reached — table ze. 7755 Polymer Specimen C Polymer D Escorin

Ao Ao (=) Je tah temperature

YY. YY. (lbs/in") (kPa) ©, (vo1v) (ov)

Geely (molecular) mm Htn CH, ve VOAT— oY aye TYA= “Yo (molecular) C,/Cs

Vig. YET Mn 1 716 710 Mw yoy YAY Mn/Mw £4,0/0.,0 £1,Y/07,A LMW/HMW eA v0 89 v,0 0% yA I 01 Tv TEA (GaQd 01/mg) 1, 7 7 8 No (L/12)) magma flow rate Density (g/cm) 13 td 1 1 7 Production rate (lbs/hr) (0) £3) (£7) (kg/hr) Yo A Approximately A Approximately a al RES A Yield Rate Pa (lb/hr/in of mould)

ANY

Pressure Altitude 00m Hey Stand up (psi') (MPa) (2%)( )2( )© Motor load (A) 1¢,0 1 oq BUR ¢ ¢ 1 (in) (cm) 5 2 79 2 v1 2 (Vv) (3,8) (VY (+ ).1) (curl) (+1) fusion fraction did not occur did not occur did not occur bubble stability Moderate Good Good Good Good Good Measurement Diaphragm (mL) (µm) 1" 8 1m 1m (Yet) 177 (5.4) Am 0 (Yet) 177 Sagittal Impingement (g) Yo.

Ya.

You YA Yoo 77 Tensile Strength toward Machine (lbs/in") (MPa) Y44. YoY. Y1 166 Support (Ww) (17Y) 0) 0 (m (vA) in the transverse direction (lb/in).

Yo.

Yo.

Ya.

Yt.

YY. Transversal v4. ov.

Yo. 10 ¥Ao ir. gaia machine tear (g/mL) (g/µm) YY Yo v1 1 7 Yt (+.AV) (+47) (V.£Y) (0. £7) (+.AY) (+.8¢) transverse (g/mL) 10; VEY 11 Yo.

AY for (g/µm) (0( )9.*( (YA) (>) (x) Ov coefficient of machine orientation (klbs/in') VY.

Voy VY. 011d4 (MPa) (AVY) (Yoh) (71) (AYV) (v¥¢) (247) transverse (lbs/in)) 1Y4 71 WA " 1 114 (MPa) ( y11e) (Very) (vA) (AAR) (M9) (AAT) AAY

Use a two-shaft Alpine extruder line 8.1 cm long (?(fas) die diameter 0.7 cm (; inch); die gap 0106 µm (£0 mil); The temperature at which the mold was set was 1007 °C (STE). In addition to the above examples; Other changes to the polymerization using the catalyst systems described in this statement include: - 1 the ability to dissolve compound 1 in a solvent; Toluene is preferred for forming the desired solution in the desired weight percentage and then used in combination with other catalyst systems. The possibility of using catalyst A in the form of a solution of concentration of 70.80 by weight in toluene and the possibility of using catalyst B in the form of a solution of concentration of 70, Y0 by weight in hexane with molar ratios of 8 to M of about 17 When the two are activated separately and then mixed with ls (parallel activation) or with molar ratios of 3 to m ranging from 7.7 to 1.0, when a sinner is activated, b is added (successive activation). Reaction heat to reduce or increase the Mn/Mw ratio, respectively. ;- Change the residence time to select the properties of the product. Large variations may have a clear effect. ve seems to use a residence time ranging from 1 hour to © hours; preferably ; hours results in Latte with good properties ©- spraying the catalyst in the reactor in such a way as to create a PPC The PPC can be created by a circulating gas flow through a 15.7 cm (7 in) tube at a rate of 1,709,560 kg/hr ver (00 lb/hr).The catalyst can be atomized by ve spray nozzel using nitrogen atomizing gas -1 Possibility of using an activator; MMAO 3A is preferred at a concentration of AY by weight in isopentane hexane hexane heptane at a feed rate sufficient to obtain a ratio of ZefAL ranging from 001 to Foo = catalyst A is mixed with 3A 100080 directly then catalyst B is added directly; Then Jax) the mixture ve to the reactor. AAY vi directly and then MMAO 3A directly and catalyst B is mixed with MMAO3A catalyst A is mixed with —A The two activated catalysts are mixed directly and introduced into the reactor. All documents described in this release are incorporated for reference. ; Including any precedence documents and/or test procedures. As can be seen from the previous general description and specific embodiments; Various modifications may be made without deviating from the principle and scope of the invention; Although 0 forms of the invention have been clarified and described. Within the scope of this invention is the use of two or more metallic compounds with a catalyst system of the metallocene type containing 15 containing one or more elements from the group of the conventional type. According to Slim, the invention contains one or more ligands and/or systems, so the invention is not intended to be identified as such.

AAY

Claims (1)

Claims 1-1 A process for the polymerization of olefin(s) (165:)58E involving the use of a catalyst composition comprising a first catalyst system containing y compound of a metal of groups ? to 1 bonded with a bidentate ligand or ¢ tridentate containing an element of the group Cua YO the ° metal atom of groups ¥ is bound to 1 with a leaving group at least one and with at least two atoms of group 0; and wherein at least one Baal atom of at least two group 11 atoms is bonded to an atom of group 10 01 of A through a bridged group ¢bridged group and a second catalyst system .system 5 1 "- process Td of claim 1 wherein the second catalyst system ¥ contains a metallocene 2 metallocene containing a bulky ih ou ¥ bulky ligand A conventional transition metal catalyst selects ¢ from the group consisting of Ziegler-Natta Cal lea ccatalysts ° ¢vanadium containing catalysts Phillips catalysts 1 1 1 Process Gd, of claim 1 wherein a metal compound containing an element of Y group 11 is a compound of a metal from groups 1 to 6. G8 of claim 1 where it chooses the bridging group of class Y consisting of a © to © hydrocarbon group (having from 1 to 10 carbon atoms) a group containing on heteroatom silicon germanium AAY vr .phosphorus and phosphorus <lead lead ¢tin ¢germanium ¢ with 11 or 1*9 where the atom from Group 1 Process of claim 0 1; halogen VE A group containing an atom of group chydrogen Y or may not bond with any heteroatom atom or group containing a heteroatom chalogen Y with a Vo toroid group or group; Whereas both atoms of the group are also bonded to a chalogen atom, a halogen hydrogen, and it may optionally bond with a cyclic group ° hehydrogen or a chydrocarbyl group, a heteroatom 1 -heteroatom containing a heteroatom. 7 where the 1-element metal compound of the claim Gag is the process —1 / group 10 of the formula: Y 7 RI] AY AVI six “1 2:4 \ 3 r 4 Low NK Rly MK. © ¢ where 04° represents 138 groups? To M 1 “leaving group separately, easy to remove group X each Jig 7 1 L” represents a number equal to zero or A “M” for oxidation state represents the oxidation state “9 dead vi L7-7&1 or L7-7&1 formal charge represents the formal charge “” 01 ¢ VT or 115 element of the group BL 11 or a group containing an element of 11 or 11 representing an element of the group I \Y ; 14 group Vr ¢ 10 represents an element of group 7 \¢ 10 represents an element of group Z Vo Cito min hydrocarbon Cio l and l each separately represent a hydrocarbon group © to V1 an atom of no more than 10 heteroatom containing a hetero-atom de gana group VY lead tin: lead germanium silicon carbon phosphorus or phosphorus 1 <hydrocarbon group may not exist or may represent a hydrocarbon group 3 9 heteroatom group chalogen halogen chydrogen 71 heteroatom YY caryl group azryl de gana alkyl group alkyl de gana and 5 separately represent RY YY alkyl group csubstituted aryl group substituted aryl group vt cyclic alkyl group Yo “cyclic aralkyl group substituted cyclic alkyl group 71 OR substituted cyclic aralkyl group 7” multiple ring system Substituted cyclic aralkyl group YA and 85 rings together; RY L and 82 may bond to each other and/or may bond Ya on Hydrogen unit US and 8 each separately may not be present or may represent RS heteroatom heteroatom chalogen halogen calkyl group alkyl group chydrogen 71 and tehydrocarbyl group nitrate or hydrocarbyl group containing An atom of chydrogen may not be present or may represent a hydrogen © © 'heteroatom or a group containing a heteroatom halogen group € )¢ halogen vi AAY Vo and 25 are of the following form: RY The operation under claim 1 where 1 - 1 12 is R! Re pie Rr? \ : 2 bonds with 7 or the alkyl group©, to a hydrogen, where “8 to” l separately represent hydrogen 0 or a group containing “heteroatom heteroatom chalide” C; to Mt alkyl group Mt £ where a carbon with no more than 560 carbon atoms forms a heteroatom heteroatom and/or a mixed cyclic group a cyclic group R any two of 1 cyclic groups where heterocyclic group 7 may be aromatic .aromatic A separately RZHRY instance group where each 87;1 of protection Gig represents operation —A 1 butyl or propyl cethyl emethyl Y and the emethyl represents RZ 9 RY methyl groups (R® where A represents the process according to claim —1 4 hydrogen and no hydrogen R ® 1 represents a metal of the group; 1 7 and 2 M represent the process according to claim 9 where —Y 1 R' 5 hydrocarbon radical represents 8 and 82 cnitrogen hydrocarbon radicals 1, 185 and 8 are not present. chydrogen Hydrogen Jia AAY va ZsL represents a metal of the group ; M represents the process according to claim 9 where 1-11, 15 and 27 are non-cihydrocarbyl radicals and 17 represents the hydrocarbyl radical 'nitrogen' nitrogen 7 present second catalyst system The process according to claim ¥ where the second catalyst system 1-1 comprises a metallocene compound containing a bulky ligand of the general formula Y L°"MQx(YZ)X, Y ; 11 represents 13 from groups to M where: (M) associated with a bulky ligand representing a bulky ligand LP °M associated with a univalent anionic ligand representing a monovalent anionic ligand © 1 cunicharged polydentate ligand L (0:) 72 forms a univalent anionic group or univalent anionic group represents a monovalent anionic group X A and “divalent anionic group q Y” or 1 equals faze represents “ 01 carbamate carboxylate represents carbamate X where VY of conservant Gag process "-1"" 1 last described in the ligand heteroallyl moiety any mixed allyl moiety “carboxylate Y Q2(YZ) unicharged polydentate ligand with multiple teeth with a single charge 1 .6 represents a metal of the groups ; to M where VY according to the element of protection A dell -14 0 metal from the group; and 17 is Bio 104 where VY is of claimant Gi, process —V 0 1 fluorenyl or indenyl group de gana Y ANY Lal 1 7- Process 885) of claim 1 wherein the second catalyst system 1 includes a conventional transition metal catalyst selected from group 1 consisting of Ziegler-Natta catalysts -Natta catalysts ¢ vanadium containing catalysts Phillips catalysts ° and combinations thereof VY 1 — Process according to claim 1 where catalyst systems include Y activator =A 1 the process according to the element i lal where yal ll i lee 5 polymerization process Y is a continuous gas or slurry phase process 7 -11 01 The Gay process of claim 1 in which the olefin(s) consist of ethylene Y and one or more other olefins. -0*1 0 Operation Gh of the protection? Where is the compound containing 3B of Y groups? to the Y associated with a bidentate or a tridentate containing an element of group Yo and the metallocene ¢ metallocene containing a bulky ligand 0° with a molar ratio of 44 ga It ranges from 44:1 to 0:94 -71 1 Process according to the claim where the metal-containing compound of groups “Y” to 7 bonded with a bidentate or triple 7-anine ligand tridentate containing an element of the group Vo and the compound AAY VA bulky ligand containing metallocene bulky ligand ¢ .001:060 to 0:01 ranging from molar ratio with compound °ANY