SA05260397B1 - A Catalyst Compositions and Methods for its Praparation and Use in a Polymerization Process - Google Patents

Abstract

A Catalyst Compositions and Methods for its Praparation and Use in a Polymerization Process This invention further relates to the use of a catalyst composition in the polymerization of one or more olefins. In particular, the polymerization catalyst system is carrier-mounted. Specifically, the polymerization catalyst includes a metallocene catalytic system containing a bulky ligand.

Description

-Y- Catalyst composition, methods of preparation and use in polymerization process

A Catalyst Composition and Methods for its Praparation and Use in a Polymerization

Process Full description Background of the invention This application is a partial application of Application No. 995700477, which has been filed. ARAMA in the Kingdom of Saudi Arabia on 1/4/77 70 AH corresponding to this invention relates to a catalyst composition and methods for preparing the catalyst composition and its use in the process of polymerization of olefins 0 bulky ligand containing a bulky ligand metallocene catalyst from a metallocene-type system a conventional transition metal catalytic system and a metal carboxylate salt if .carboxylate metal salt advanced research in polymerization and catalysis has made it possible to produce multiple new polymers With improved physical and chemical properties suitable for use in a wide variety of products 0 and distinct uses.With the development of new catalysts, the choice of type of polymerization process (in solution, slurry, high pressure or gas phase) to produce a specific polymer has greatly expanded. Also, advanced research in polymerization techniques has led to the creation of highly productive, economically enhanced and more effective processes.An example of this advanced research is the development of technology using systems containing a large ligand.Apart from these catalytic metallocene Metallocene type 1 polyolefin Advanced technical research issues in the polyolefin industry still exist Common and novel intractables associated with process workability. for example; The processability of plates is considered as one of the intractable problems. df in a gaseous phase or slurry phase can form dirt

A, for example; Fouling may result on reactor walls in a continuous process in the sludge phase; which is a Ghee surface for heat transfer; This causes several operability issues. Poor thermal transfer during polymerization may cause the polymer particles to stick to the reactor walls. These polymeric particles may continue to polymerize on the walls and may lead to premature shutdown of the reactor. as well; A small amount of the polymer may dissolve in the reactor diluent and re-deposit on the metal heat exchanger surfaces for example; depending on reactor conditions

In a typical gas phase continuous process; A recycling system is used for several reasons, including the removal of heat generated in the process by polymerization. Fouling, lamination, and/or static generation in a continuous gas-phase process may result in the various reactor systems not operating effectively. For example Jl) the refrigeration mechanism in the recycling system and the temperature probes used to control the process and the distribution board may perform; in case

This led to an early failure of the reactor. Several patents in the technology have addressed operability problems in various processes and offered solutions. for example. US Patents Nos. 4,797,897, 26,751 r.d.m.€, and 0.751,659 describe techniques for reducing static generation in a polymerization process by adding water, alcohols, ketones, and/or additives inorganic chemical eg to process. The International Patent Bulletin pursuant to PCT No. 97/149771 of YE April describes NAVY quenching the particulate matter that may cause lamination by adding an inert hydrocarbon to the reactor; US Patent 0.177.767 describes a new type of distribution plate for use in gas-phase reactors that contain a fluidized bed. The International Patent Bulletin according to PCT No. 50 96/078057 describes avoiding the addition of a scavenger to the reactor. US Patent 2.477.177 describes The use of acoustic waves to reduce lamination and the US Patent 0 ...0 and the European Patent AT + 047 YOY describe the addition of an activity inhibitor to the reactor to reduce

And

conglomerates. US Patent YEE 0.1 (0.1) relates to feeding a complementary monomer directly into the supra bed reactor to avoid fouling and to improve the quality of the polymer US Patent 5,171,514 describes the use of an oligomer removal system to reduce spread plate fouling Production of gel-free polymers European patent AL 0 407 describes 111 of October 77, 1991 © Adding antistatic agents to the reactor to reduce the amount of plates and blocks. The US patent describes 4,017,594; adding a surfactant; eg Ae gana PFC 000+ to the reactor to reduce fouling US Patent 5,077,748 describes the addition of an electrostatic agent with a liquid carrier to the polymerization zone of the reactor US Patent eu oY (0.8) describes the use of a conventional ge 0 catalyst system Ziegler-Natta type J gana Ziegler-Natta with titanium or magnesium Cum A selection of anti-electrostatic agents are added directly to the reactor to reduce fouling The US patents E EAL and 0.274.441 describe the resulting reaction product The use of a conventional titanium catalyst of the Ziegler-Natta type with an anti-electrostatic agent to produce ethylene polymers with a high molecular weight (faa). The American patent ve 2..87.158 describes the addition of an amount of carboxylic acid depending on The amount of water in the process of polymerizing ethylene using organometallic catalysts containing titanium and aluminum in a liquid hydrocarbon medium. The American patent 7.19.15 describes a reedig process using a non-polar hydrocarbon diluent using a conventional catalyst of Ziegler-Nata or Phillips type and Ce SSH

© Organic acid with a molecular weight of at least Xoo Various other known methods for improving workability include coating polymerization equipment eg treating reactor walls with chromium compounds as described in US Pats 4,077,721 and 5,871,770 and injecting agents diversified in process, for example, IPP No. 97/478494 according to ve patent issued in 19959 pad 11 describes the feeding of a portable soluble catalyst system of type

- 0 metallocene to a material-poor area in the polymerization reactor and injecting algae-blocking agents and anti-electrostatic agents into the reactor and controlling the polymerization rate, particularly at the start of

Run the process and rearrange the reactor design. Other patents in the technology to improve process operability describe modification of the catalyst system by preparing the catalyst system in several ways. for example; Methods in the technique include mixing the components of the catalytic system in a specific order, manipulating the ratio of the different components of the catalyst system, varying the contact time and/or temperature when mixing the components of the catalytic system, or simply adding different compounds to the catalytic system. These techniques or combinations thereof are described in the handouts. Specifically, preparation procedures and methods for producing bulk ligand-type metallocene catalytic systems and specifically bulk ligand-containing metallocene catalytic systems with low fouling capabilities and better workability are described in the technique. Examples of such patents include ISPM No. 91/118951 issued in YT April 1947 describing an antielectrostatic agent as a component of a portable catalytic system for reducing soiling and lamination in a gaseous, reactive or liquid polymerization process and Patent 1 US 2,787,748 relating to the prepolymerization of a metallocene catalyst or a conventional Ziegler-Natta catalyst in the presence of an electrostatic agent and US patents .2 and 77..78;. and US Patents 8.577.951 and 0.147.847 describing the chemical binding of non-coordinating anionic activators and supports | © US Patent 6 describing polymer-bound metallocene catalytic systems and US Patent 0 describing a metallocene catalytic load on an olefin and unsaturated silane copolymer and IPC PCT prospectus Patent Cooperation No. 97/6186 issued in Ye February 1949 describing the removal of organic and inorganic impurities after the formation of the catalytic metallocene of the same type and International Patent Application Bulletin 97/197507 issued

-91 of May 1, 1999 Describing Easily Carryable Metal Complexes and PCT International Patent Application Bulletin No. 97/777716 of © 1 July VARY Relating to the Formation of a Portable Transition Metal Compound in Presence of an unsaturated organic compound containing at least one terminal double bond and EP 174 82-411 describing the use of a metallocene catalyst and an activating co-catalyst in a polymerization process in the presence of an electrostatic agent containing nitrogen nitrogen. These possible solutions may reduce the level of soiling or lamination somewhat; However, some are prohibitively expensive and/or may not reduce smudging and lamination to a sufficient level to successfully run a continuous process, especially a commercial or large-scale operation.

01 Thus it is advantageous to devise a polymerization process with continuous workability and enhanced reactor workability while producing new and improved polymers. It is also highly advantageous to devise a continuous running polymerization process with more stable catalytic yield, low fouling or lamination ability and increased run life.

| General description of the invention

Vo This invention provides a method for making a new and improved catalytic composition for use in a polymerization process. The method includes steps to combine, contact, synthesize and/or blend a catalyst system preferably a portable catalyst system with a carboxylate metal salt and in asl embodiments; The catalyst system includes a transition metal catalyst compound of a conventional type. In the most preferred embodiment the catalytic system includes a metallocene catalytic complex containing a large ligand.

© It is useful to combine the catalyst system with the carboxylate metal salt in any polymerization process of the olefin “Taah. Preferred polymerization processes include the gas phase or sludge phase processes and most preferably the gas phase process.

and in embodiment; The invention provides a method for making a catalyst composition useful for the polymerization of olefin

one or more where the method includes incorporation, contact, synthesis, and/or blending of a polymerization catalyst with

ve at least one carboxylate metal salt. and in embodiment; is considered catalytic

.y - polymerization is a transition metal polymerization catalyst of a conventional type and the best is a portable transition metal polymerization catalyst of a conventional type. and in the most favorable embodiment; The polymerization catalyst is a metallocene catalyst containing a bulky ligand and most preferably a portable metallocene polymerization catalyst containing a bulky ligand. In a preferred embodiment; The invention relates to a catalytic composition comprising a catalyst compound, preferably a transition metal catalyst compound of a conventional type, and preferably a metallocene catalyst compound containing a bulky ligand, an activator and/or a co-catalyst, a carrier and a carboxylate metal salt, and in the most preferred method of the invention. ; Synthesize the carboxylate metal salt 0 preferably dry synthesize and most preferably dry synthesize id i with core or cae provided that the portable catalyst system or polymerization catalyst includes a carrier. In this most preferred embodiment the polymerization catalyst includes a metallocene catalyst complex containing at least one large ligand, an activator and a support. Also in the HAT embodiment; The invention relates to a process for the polymerization of one or more olefins in the presence of a catalyst composition comprising a polymerization catalyst and a carboxylate metal salt. Conventional and/or a metallocene catalytic compound containing a large ligand. and in a preferred method of making the catalyst composition according to the invention; The method includes the steps of combining Yo, a bulky ligand-containing metallocene catalyst, an activator, and a carrier to form a bulky ligand-containing metallocene catalyst system and contacting a metallocene bulky-containing catalyst bulky with a carboxylate metal salt and in the most preferred embodiment the portable catalyst system is a metallocene containing bulky ligand los vo carboxylate metal salt in an intrinsically dry or dehydrated state. | stuttering

ph = in embodiment; This invention provides a method for the polymerization of one or more olefins in the presence of a polymerization catalyst that has incorporated, contacted, synthesized or mixed with at least one carboxylate metal salt. Description Ladi dad Bao This invention relates to a method for making a catalyst composition and the catalyst composition itself. This invention further relates to a polymerization process having improved workability and production capabilities using catalyst synthesis. Surprisingly, it was discovered that the use of a carboxylate metal salt in combination with a catalyst system substantially improved the polymerization process. It is particularly surprising when the catalyst system is carried on a support material, and even more so when the catalytic system includes a metallocene catalyst system containing a large ligand, and even more so when the catalytic systems are of the metallocene type. which contain a more active bulky ligand and/or have a higher degree of co-monomer incorporation. Although he does not wish to be bound by any theory; However, these catalysts are believed to be metallocene ve and contain a large ligand that is more susceptible to lamination and/or fouling. It is believed that very high efficiency catalysts may produce intense heat that is confined to the growing polymer particles. It is theoretically believed that these extreme conditions lead to higher levels of lamination and/or fouling. It is also believed that the polymers resulting from metallocene catalysts contain large ligands that form durable polymeric sheets (Jaa) and thus it is difficult to break and remove any of these sheets that may form in the reactor. In addition to that; It was highly unexpected that high-density fractional melt index polymers could be produced using a combination of a polymerization catalyst and a carboxylate metal salt with improved workability. This discovery was Loge's in particular because it is known in the polymer industry that these types of jade vo are difficult to produce when looking at the workability of the process.

The use of the polymerization catalysts described below in combination with a carboxylate metal salt significantly improves process workability, significantly reduces lamination and fouling, improves catalyst performance, and improves the crystal shape of polymer particles without AY negative effects on polymer physical properties and range yieldability. wider than polymers. 0 Catalyst Components and Systems All polymerization catalysts including transition metal catalysts of the conventional type are suitable for use in the polymerization process according to the invention. However, processes using metallocene-type catalysts containing a bulky ligand and/or a bridge bulky ligand are particularly preferred. The following is a non-specific description of various polymerization catalysts useful in this invention. CL lia. Conventional transition metal The transition metal catalysts of the conventional type include those of the conventional Ziegler-Natta type and the chromium chromium catalyst of the Phillips type which is well known in the technique. Examples of transition metal catalysts of the conventional type are described in US Patents Nos. 4,119,774, 64 No., 4/787, 6375, 7/19, 4 No, and £.970v8Y 6 which are all incorporated herein in full for reference. As a reference, the transition metal catalyst compounds of the conventional type that can be used in this invention include the transition metal compounds of groups * to A and preferably −b to 1b of the periodic table of chemical element distribution. : MRy where © does not represent a metal chosen from groups “B to A” and preferably group Gf and the best is titanium ¢titanium and © represents a halogen atom or a hydrocarbyloxy group x represents the valency of the metal 14 Examples of R include but are not limited to alkoxy, phenoxy, bromide, chloride and fluoride 100:06.itd include conventional transition metal catalysts where Jig M is titanium titanium for example

-1. - but not limited to Ti(OC,Hs)Cl3 5 Ti(OC,Hs)sCl 5 TiBrs 3 TiCly and Ti(OC4Ho);Cl and

Ti(OC12Hys)Cls 5 TiCla.1/3AIC; 5 Ti(OC;Hs),Br, 5 Ti(OCsHy),Ch Transition metal catalyst compounds of a conventional type based on donor complexes suitable for use in titanium and magnesium were described for electrons from the invention. » For example in US Patents 4,707,888 and 4,707,015 which are incorporated herein in full for reference. A derivative (ethyl acetate) is particularly preferred. UK Patent Application 14811016 (cthyl acetate)s describes MgTiClg which is incorporated herein for reference; 7.01.0 Miscellaneous Conventional Catalyst Compounds Examples of vanadium-containing conventional catalyst compounds include, but are not limited to, vanadium trihalides ala vanadium 0 700603 Mql 700 and vanadyl alkoxides and vanadyl alkoxy halides vanadium tetra-halide and (and 70)00211 and butyl vanadium tetra-halide represents butyl Bu where the alkyl VCI3 (Obu) such as 17014 and vanadium alkoxy halides and alkoxy halides vanadium and vanadyl acetyl acetonates J Ba (AcAc) and (AcAc): 77100 where V(AcAc); Such as chloroacetyl acetonates 00 Preferred traditional vanadium catalyst compounds include vanadium 80801 acetonate hydrocarbon radical chelate representing the R hydrocarbon moiety where VOCL-OR, BL© and VOCs 1 contain from Aromatic or aromatic aliphatic hydrocarbon, preferably an aliphatic hydrocarbon crack, butyl isopropyl, isopropyl phenyl, phenyl ethyl ethyl Jie carbon carbon atoms 0 to tertiary iso-butyl and isobutyl n-butyl and propyl © Khalil Khalonat and Ad. onaphthyl cyclohexyl naphthyl cyclohexyl hexyl butyl vanadium. Examples of conventional chromium catalyst compounds include; which are often referred to as “Phillips catalysts, which are suitable for use in this invention, are CrO, chromocene, silyl chromate, and chromium chloride.

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chromium-2-ethyl-hexanoate and 7-ethyl-hexanoate chromium (CrO,Cly) chromyl chloride and the like. She described (Cr(AcAc);) chromium acetylacetonate and chromium acetate.

Unspecified examples in US Patents Nos. 7,188,771, 717..34, and 2,170 are incorporated herein for reference. :

Other conventional transition metal catalyst compounds and catalytic systems suitable for use in this invention are described in US Patents Nos. 4,176,877 and 2,307,565.

and 4,207,017 and 0,737,777 and EPP 02 416 815 e f

AT + £470FT which are all incorporated into this statement for reference. The transition metal catalysts of the conventional type according to the invention may also have the general formula MME

0 where 14 is 14 and/or 148 and/or Ca and; represents a number from 1# to ? M75 represents a Lili metal chosen from Ti and/or 17 and/or Zr and represents a halogen atom, preferably Cl, Br, or

dl nor is it symmetric or different and Jia has a halogen atom, either alone or in combination with oxygen, oxygen, 1182, -0, -88, -008, or 405008, where Jia is the hydrocarbyl cleft, and in particular An alkyl moiety or an aryl cycloalkyl radical

cycloalkyl yo or arylalkyl anion or acetylacetonate anion by an amount that achieves a valence state of 14 yen representing a number ranging from +00 to 71 and 5 representing a compound

Electron donor compound chooses from the following classes of compounds: 0) Esters of ¢organic carboxylic acids (b) alcohols ¢alcohols

(c) ethers (d) amines (—a) tamines esters of carbonic acid

of carbonic acid v. ¢nitriles (g) phosphoramides (h) esters of phosphoric acid and phosphorus

40 (i) Jo phosphorus oxy-chloride Examples of compounds that apply to the above formula include but not limited to: Mg3Ti;Clj,.7CH3COOC,H;s s MgTiCls2CH3;COOC,Hs and MgTiCls. 6C,HsOH

Yo, MgTiCls.100CH30H, (tetrahydrofuran) MgTiCls.tetrahydrofuran MgTiCls., and

Shy - MgsTizCli2.6CsHsCOOC,Hs 5 MgTipCliz. 7CeHsCN and MgTiClg.2CH;COOC,Hs MgTiCls(OCH;).2CH3COOC;Hs 5s MgTiCls.6CsHsN 5 MgTiCIsN(CeHs). 3CH;COOC;Hs 5, MgTiBr,Cls.2(C2Hs);0, MnTiCls.4C,HsOH, and a) 5 MgsVaClip. 7CH;COOC;Hs hesidophore MgZrCleA(0) 1187:0164 tetrahydrofuran o Other catalysts may include cationic catalysts ACH Jie and other cobalt and iron-fron catalysts are well known in the technique. usually; These conventional-type transition metal catalyst compounds, with the exception of some conventional chromium catalyst compounds, are activated using one or more of the conventional co-catalysts described below. 0 A conventional-type co-catalysts and Jac has conventional-type co-catalyst compounds for the conventional-type transition metal catalyst compounds shown above with the formula MM VK OR pc where MP represents a metal belonging to groups 1a, ?a, and “B” and “a” from the periodic table of the elements 5 MY represents a metal from group 1a of the periodic table of the elements and represents a number equal to zero or 1 and each X2 represents any halogen atom 0 and © represents a number ranging from zero to * and every 87 Jaa is a monovalent hydrocarbon radical or hydrogen and © represents Jae ranging from 1 to 4, where b minus » equals at least 1. The co-catalysts have Other conventional organometallic catalysts for the above conventional type transition metal catalysts have the formula 2283, where MP is a metal chosen from groups 1, ?a, b, or y. Lithium and sodium barium” 5 Ll 5 beryllium boron aluminum aluminum zine cadmium ks gallium equal to 1 or Gans oF the MP equivalence which in turn usually depends on The specific group that tM? belongs to and each 13 represents any monovalent hydrocarbon moiety. Examples of organic metal co-catalysts of the conventional type include vo of groups 1a, ?a, and ?a which are suitable for use with conventional-type catalysts

110 -: Described above, for example but not limited to, methyllithium, butyllithium, Jb butyllithium, dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium, diethyl zinc, 016112106, and third P-butyl aluminum manufactured by 71At-1-0, diisobutyl ethylboron, diisobutyl ethylboron, diethylcadmium, Jb gre, zinc di-n-butylzine, and tri-n-amylboron In particular, the aluminum alkyls, Jie aluminum alkyls, tri-hexyl-aluminum, J-triethylaluminum, trimethylaluminum, and tri-isobutylaluminum, include the co-catalyst compounds of the conventional type. Others 01 mono-organohalides and hydrides of group A metals and mono- or di-organohalides and hydrides of 568 group IY metals and include examples of co-catalytic compounds of a conventional type Such as but not limited to di-isobutylaluminum bromide, isobutylboron dichloride and methylmagnesium chloride m | methyl magnesium chloride, ethylberyllium chloride, ethyl- calcium bromide, di-isobutylaluminum 06, methylcadmium hydride, diethylboron hydride, hexylberyllium hydride hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride © | butylzine hydride, dichloroboron hydride, di-bromoaluminum hydride, and bromocadmium hydride. A fuller description of these compounds is contained in US Patents Nos. 3,771,007 and 9,047,416 which are fully incorporated into this

ve statement for reference.

“vg - For the purpose of this description and the appended claims, transition metal catalyst compounds of the conventional type exclude those metallocene catalysts containing a large ligand described below. For the purpose of this description and the accompanying claims, the term “co-catalyst” when used in this statement refers to conventional-type co-catalysts or to conventional-type organometallic cocatalyst compounds. Compounds and catalytic systems of the metallocene type containing a bulk ligand for use in combination with a carboxylate metal salt of the present invention are described below. metallocene catalytic composites containing bulky day) including metallocene catalytic compounds containing a bulky 0 ligand generally interlayer compounds containing one or more bulky ligands including Structures of the type cyclopentadienyl ila or other similar functional structure Jue pentadiene, cyclooctatetraendiyl (Als) and imides .imides Typical metallocene compounds containing a large ligand are generally described as containing a ligand. one or more with the ability to bind to a transition metal ae with an eta bond at the © position; usually ligands or moieties derived from cyclopentadienyl in combination with a transition metal choosing from the − to A groups preferably the −, © or + groups Or from the lanthanide and actinide series of the periodic table of elements.These examples of metallocene catalytic compounds and systems containing a large ligand and catalytic systems are described for example in US patent numbers (Kave, Malala and LOAVES 40744 8.47 and to meet B, Lm 17, 17414, 44431, and 6701 M 5 O.YYA.EVA Ro Malakta and Tekla and O.YVAANYA and ¢ 9.041 and .5.7704.4 and o.¥EV..Yo and 17No 2.8 and 0.784.759 ot ©.Y9).YAQ and 0.¥44.1Y1 and ot ALY 0.491.717 and 17 Yo 17R ©.Y9).YAQ and 0.¥44.1Y1 and ot ALY 0.884.020, 2.171.177, and YYW

-100-:

0. TAL. 4A Rowe 1 aphids and jaws f 8/17 f 0 84 .8.7/17 f

Is the pain exacerbating the pain 4 of the strife and the pain of the mother for the thousand Fa and

| 4 and 87 no, no, no. and 2,727,664 which are all incorporated into this statement fully for reference. as well; All of the following patents are fully incorporated for reference

0 - For reference purposes of describing metallocene-type compounds and catalyst systems containing

On a huge band, which is the European Patent Numbers (Vou) 09. Horo 700777

AYY 4A « 170 46 4 A Mf + VEY 74 4 Bl + £A0 AYY SBI 2.E F

7 08 810 and PCT International Patent Publications Nos.;

Ed Hour AY/ Try 5 Lectures

It is AV[YeoAY ri 11h to neighbourhood, the burial of the akhah 4 talatah and 14 akh

In the embodiment of the invention; represent catalyst compounds of the metallocene type containing a bulky ligand according to the invention with the formula: 6 (0)

1 where M represents a metal selected from the periodic table of elements and may be selected from groups from “to 0” and it is preferable to be a transition metal from the group; or © or 1 or a metal chosen from the lanthanide or cactinide series, and it is better to represent 14 transition metals chosen from the group ; And the best is zirconium, hafinium, or titanium, which represents each of LA and 17 huge ligaments, including ligands derived from cyclodienyl penta

cyclopentadienyl Y. or cyclopentadienyl-derived ligands bearing a substituent or cyclopentadienyl-derived ligands containing a hetero-atom or carrying a Say thereof or cyclopentadienyl-derived ligands bearing a substituent of Hydrocarbyl or Jie moieties Indenyl ligands, benzindenyl ligands, fluorenyl ligands, thachamine hydrofluorenyl ligands

octahydrofluorenyl | +0 and cyclooctatetraendiyl ligands and aznyl ligands

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azenyl and borabenzene ligands and the like, including their hydrogenated forms. *1 and 12 may also represent any other ligand structure that has the potential to bind to 14 eta-links at the © position; For example, LA and 1 contain one or more heteroatoms eg nitrogen, silicon 2, boron, and germanium | 0 and phosphorous in combination with carbon atoms to form a ring structure; For example an additional 'heterocyclopentadienyl' ligand and moreover; Jim lists both *1 and 1 as well as other types of bulky ligands including but not limited to amides 55, phosphides, alkoxides, aryoxides 1065, imides, carbolides, and borollides 0 porphyrins, phthalocyanines, massive corrins, and other large-cyclic polyazomacrocycles. Both fennel and LB have varieties

Same or different from a large bonded ligand with 14 pi bonds. Both 1 and LB may carry a substituent from a combination of R groups Examples of R substituents include but are not limited to hydrogen, linear or branched ve alkyl moieties, or cycloalkyl moieties cyclic alkyl, alkenyl, alkynl, aryl, or a combination thereof containing from 1 to Ye carbon atom, or other substituents containing not more than 50 atoms other than hydrogen hydrogen can also carry substituents. Examples of R alkyl substituents include, but are not limited to, methyl groups, ethyl alcohol, propyl Jus, butyl, pentyl hexyl, cyclopentyl Als Jiu 0 or cyclohexyl cyclohexyl, benzyl or phenyl, halogens and the like; Including all the isomers, for example, tertiary butyl and isopropyl. ethyl difluroethyl iodopropyl bromohexyl vo chlorobenzyl hydrocarbyl 70:00:71 including trimethylsilyl

And he turned around

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071 Je trimethylgermyl and the like Ly methyldiethylsilyl and organometalloid radicals bearing a halocarbyl substitute including tris(trifluoromethyl)-silyl -silyl and methyl-bis silyl (difluoromethylsilyl °, bromomethyldimethylgermyl and the like, and difluoromethylgermyl moieties, including dimethylboron For example, 001000860 binary substituent Ley moieties including dimethylamine, dimethylphosphine, diphenylamine and methylphenylphosphine, and UL achalcogen moieties including 1-methoxy methoxy, ethoxy, propoxy, phenoxy, methylsulfide, and ethylsulfide. Non-hydrogenated R substitutions include 08 carbon atoms, silicon silicon, nitrogen, and phosphorous oxygen, tin, germanium and the like including but not limited to olefins Jedd olefinically unsaturated substituents | 0 vinyl terminal ligands eg but-3-enyl or 7-vinyl 2-vinyl or 1-hexene (1) and so on; at least two groups of 8 are attached preferably Two adjacent groups of USER Cyclic structure containing from 4 to Ye atom choose from carbon or nitrogen or oxygen or phosphorous or silicon or germanium a sla yal or © _ boron or a combination thereof.Also an R group such as 1-butanyl may form a bond

Sigma bonds with metal M, and other ligands may bond to the transition metal; Sia is a leaving group denoted by 0. Where © may each separately represent monoanionic labile ligands bound with M sigma bond. Examples of 0 include but are not limited to weak bases such as amines, phosphines, ether, or

Carboxylates, dienes, or hydrocarbyl moieties containing from 1 to 10 carbon atoms, hydrides, halogens, and the like, and combinations thereof. Other examples of Q-slices include the aforementioned substituents of the R-slice | described above and include cyclohexyl, heptyl, tolyl, trifluromethyl Jie, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy and propoxy phenoxy, di(11-methylanilide) bis(N-methylanilide), and dimethylamide

dimethylamide, di-Jie phosphide, dimethylphosphide, and the like. In addition to Jedd cally catalyst compounds of the metallocene type which 0 contain a large ligand according to that invention where TA and 15 represent two moieties bridged to each other by means of a bridging group denoted by H. These bridge-linked compounds were known as metallocene bridge catalytic compounds containing a large ligand. Examples of bridge group A include but are not limited to bridge moieties chosen from at least one of the atoms of group VE; Jie, for example, Vo is carbon, oxygen, oxygen, nitrogen, silicon, germanium, tin, preferably carbon) s— SV, silicon, germanium germanium and most preferably silicon silicon Examples of other m bridge groups include but are not limited to dimethylsilyl, diethylsilyl, methylethylsilyl and trifluoromethylbutylsilyl | 0, bis(trifluoromethyl)silyl, di-n-butylsilyl, di-n-butylsilyl, silylcyclobutyl, di-iso-propylsilyl, di-i-propylsilyl, and dihexyl cyclohexylsilyl di-cyclohexylsilyl di-phenylsilyl cyclohexylphenylsilyl t-butyleyclohexylsilyl t-butyleyclohexylsilyl di-t-butylphenylsilyl di-t-butylphenylsilyl di-ve (para-tolyl) di(p-tolyDsilyl Jib) dimethylgermyl and diethyl

14 - Diethylgermyl, methylene, dimethylmethylene, diphenylmethylene, diphenylmethylene, ethylene, JAY 01, ethylene 1,2-dimethylethylene, 7-0-diphenylethylene, 1,2-0 diphenylethylene ¥¢ 1-tetramethyl 1,1,2,2-tetramethylethylene (ull) and diphenylethylene dimethylenedimethylsilyl and methylenediphenylgermyl methylenediphenylgermyl methylamine and phenylamine cyclohexylamine, methylphosphine, phenylphosphine, cyclohexylphosphine, etc. In another embodiment, the catalyst compound of the metallocene type containing a large ligand according to the invention has the formula: (Y) (CsHagR1)AX(CsHa-aROMQg-2Ve), where M is a transition metal selected from groups; and * and 1, Jia (CsHagRa)s, a massive cyclopentadienyl-derived ligand with or without substituents attached to [l] and represents all 8 that may be the same or different; hydrogen atom or substituent group containing not more than +0 non-hydrogen atom or hydrocarbyl hydrocarbyl ve with or without substituents containing 1 to Te is a carbon atom or combinations thereof, or two or more carbon atoms bond with each other to form part of a ring or ring system with or without substituents containing from 4 to 0 carbon atoms Ag carbon Represents a moiety containing one or more atoms or a combination of carbon, germanium, silicon, tin, phosphorous, or nitrogen that binds the Cpls of (CHuRg ) © Bridge and more specific A examples may represent, but are not limited to 18000, 0251142511 3 10025110020, 10266, 202518266, 2026620, 12011, 120, R,CR'N, 0201407, R',SiR'N, 251 f R'; ve halocarbyl carries a substituent or or a semi-metallic organic compound that carries a substituent of

L-hydrocarbyl or a semi-metallic organic compound bearing a substituent of a boron-substituted halocerbyl boron or a disubstituted pnictogen or a chalcogen bearing a substituent or a halogen representing JS 0; which may be the same or different; A linear, cyclic, or branched hydrocarbyl hydride or hydrocarbyl with or without substituents.

0_of which contain from 1 to *0 a carbon atom, a halogen, alkoxides, aryloxides, amides, phosphides, or any anionic ligand Another monovalent ligand or its terminator combination may also form two groups of © an alkylidene ligand, a cyclo-metal hydrocarbyl ligand, or a Cua “sal divalent anionic chelating ligand”.

Jag 0 is an integer representing the formal oxidation state of 14 and not an integer choosing from zero, 1, or ? or © or; represents the degree of commutation and * represents an integer equal to zero or .1 and in an embodiment of the invention; Metallocene catalysts containing a large ligand include those where the R substituents on the large ligands LA and 17 5 (CsHimRe) of formulas (1) and (1) carry a similar number or different substituents on both ve large ligands.In a preferred embodiment, a metallocene-type catalyst containing a massive ligand of formula x dua oY) is equal to 1. Other metallocene-type catalysts include metallocene that contains a large ligand and is suitable for use in this invention. Bridge compounds of the type metallocene Y- contain a hetero-atom and a single massive ligand. Examples of such catalysts and catalytic systems have been described for example in International Patent Publications pursuant to PCT Nos. 17/777, SAE VATA 1/1707, ag/Youn, 5/744, 97/156507 and US Patents Nos. 5..87.4978 and EVA 50. AT.ATY .40.400 4401 8.1, 8.777.446, 0.115.400 and ve Publication European Patent No. EV 4780 + 8-E which are all incorporated into this statement in full form

“wn-

for reference as a reference. Other metallocene catalysts that contain a bulky ligand and are suitable for use in this invention include those described in the US patents (go TEANY numbers Kg m and EAE lago: 0 qo 47 and klah 5 reticence rtnala and 7430 and © SOF EVE 70/401 and 0.777.744 and the International Patent Publications according to the Patent Cooperation Treaty No. 17/4771 R. Kathav/17 and 46 1 no / and 14 and the European Patent Publications No. OVA AYA, Hamar 090 3A=+ TFA J8” 7E +-QZO 27/7 AVI +-1E which are all incorporated into this statement for reference.

mechanism.

1 and in another embodiment according to this invention; The metallocene-type bridging catalysts containing a hetero-atom and a single large ligand that are suitable for use in the present invention are represented by the formula:

0 log bl 4 wl 0 where M stands for Ti or Zr or (CsHsyaRy)s HE stands for a cyclopentadienyl Vo ring or ring system bearing 1 to © substituent groups and “ “x equals zero or 1 or 1 or dv ; Or © which represents the degree of substitution and each substituent R represents separately a moiety chosen from a class consisting of hydrocarbyl moieties containing from 1 to 10 carbon atoms and hydrocarbyl moieties having substituents containing from 1 to Yo, a carbon atom, where one or more hydrogen atoms are replaced by a halogen atom or semi-radicals.

© Metallic bearing a hydrocarbyl substituent having from 1 to Yo a carbon atom Cua carbon

The semimetal is chosen from the group 1 elements of the periodic table of the elements or from the halogen moieties

“yy - halogen or Jae (CsHs.yxRyx) represents a Gus cyclopentadienyl ring Two adjacent groups of 1 link to form a ring containing of ; to 10 carbon atoms to produce a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl J— su sla, or 0-octahydrofluorenyl (R71) 5 represents a ligand containing a hetero-atom, where J represents an element with a coordination number of ? Choose from group 0 of the periodic table of the elements or an element that has a coordinating number of 7. Choose from group 16 of the periodic table of the elements, preferably nitrogen, phosphorous, oxygen, or sulfur 0, as it is considered Nitrogen is the most preferred, and each RY separately represents a moiety chosen from the class consisting of hydrocarbyl moieties containing from 1 to 10 carbon atoms, where one hydrogen atom or Most halogen atom ys halogen equals zero or 1 and "'z" represents the coordination number of element J and each © separately represents a monovalent anionic ligand such as halogen, hydride Vo, or hydrocarbyl hydrocarbyl containing from 1 to Y carbon atom with or without substituents or an alkoxide or an aryloxide or an amide or a phosphide provided that two groups of © represent the alkylide moiety alkylidene, cyclometal hydrocarbyl, or any other divalent anionic chelating ligand and “may be zero, 1, or ?; A Jia Ye, a covalent bridge group containing an element chosen from group 11 or V The periodic table of the elements includes, for example, Jie, a dialkyl moiety, an alkylaryl moiety, diaryl silicon, germanium alkyl Jl, aryl phosphine, or amine or hydrocarbyl moiety such as methylene, ethylene, and the like;

Yy - - - A represents the Lewis base, Jie Lewis base, diethylether, tetrachylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, and trimethylphosphine. trimethylphosphine, p-butylamine, n-butylamine, and the like, and “represents a number ranging from zero to.” In addition, 0 ¢ L' may be associated with any of the R, R', or ny splits Q equal to zero, 1, X, or Y . In another embodiment the metallocene macro-ligand catalytic complex is an overlay of a transition metal and a pi-bonded ligand bearing or without substitutions and one or more heteroallyl moieties such as those described For example, in the two American patents Nos. 5,577,787 and 01 5.3/6 and the European patent FYYo .-1s that Canada is all in this statement for reference. It is preferable that the catalyst compound be of the metallocene type, which contains a large ligand; Any cmonocycloalkadienyl catalyst with one of the following two formulas: [m a 27 ; (5) or 7 M~—(A), | \/ 0X20 AM where M represents a transition metal chosen from the groups; Or © or + preferably titanium or zirconium or hafinium and most preferably zirconium or

Cv - hafnium Ls ¢hafinium has a ligand linked to any bearing substitutions that are devoid of it coordinately linked with M preferably L represents a huge cycloalkadienyl ligand, for example huge ligands of cyclopentadienyl or indenyl or fluorenyl and it is possible with one or more substituent group of hydrocarbyl -0- and each © selects separately from the category consisting of tcarbon carbon atom Ye to 1 containing from 0 represents © or 5 and preferably the carbon Ys foxygen, -J8©- and -5- and preferably the oxygen NR- and 1L 5-PR; and SiR; sCR335-NR; and 7 chooses from the category consisting of +01 and carbon 2 the 108-Q tas and aryl-anah groups carry substituents or are devoid of terminators, provided that when selected from the category consisting of -NR; 5-OR and 88- and —PR, 5-SiR; and -11 thanks to that

Ast) preferably 1 or 1 and “ equals NR; Selects 2 from the category consisting of -01, 0-, and ve. A binary anionic group. By A represents a monovalent anionic group when « equals ? or valence when “ is equal to 1 and preferably A represents a carbamate moiety, a carboxylate moiety, or any other heteroallyl moiety described for moieties ©, 17, and 7; Each R separately conveys a group containing carbon, silicon, nitrogen ve, oxygen, and/or Cus phosphorous One or more groups may bond From substituent groups L and thanks to the fact that R represents a hydrocarbon group containing from 1 to 71 carbon atoms and the most preferred alkyl group is a cycloalkyl or aryl One or more groups may be associated with the alternative. A; And 1 represents a bridge group chosen from the category consisting of the alkylene group arylene cb Js alkylene © containing from 1 to 10 carbon atoms that may carry a substitute of carbon or one or more hetero-atoms or germanium germanium or silicon 11:00 and alkyl phosphine God and «represents a number ranging from? To 1 and preferably who? to LS, 1 preference? or?. In formulas (£) and (0), the auxiliary substituent formed by groups ©, 7 and Z sje Yo of a unicharged polydentate ligand exerts pressure

“Yo - electronic effects due to its high polarizability; A Blas for the .cyclopentadienyl ligand and in the most preferred embodiments of the present invention; 5-carbamates and di-substituted carboxylates are used. Examples of such catalytic compounds include the metallocene which has a large ligand on 0 | To name a few, tri (Di-Ji carbamate) J indenyl zirconium tris(diethylcarbamate), tri (tri-Jia acetate) indenyl zirconium tris(trimethylacetate) and tri(para-) Jaw indenyl zirconium tris(p- Ss toluate) (benzoate) indenyl zirconium tris(benzoate) and tris(trimethyl acetate) (1-methyl (Jip —n) Zirconium-1( methylindenyl)zirconium tris(trimethylacetate) 01 and tris(J carbamate) Jha indenyl) zirconium tris(diethylcarbamate) and tris(trimethyl acetate) (methylcyclopentadienyl) zirconium tris(trimethylacetate), cyclopentadienyl tris(trimethylacetate) (Als), and tetrahydroindenyl zirconium tris(trimethylacetate) and (pentamethylcyclopentadienyl) zirconium tris(benzoate). Preferred examples include indenyl zirconium tris(diethylcarbamate) and tris(diethylcarbamate). (Jima) indenyl zirconium tris(trimethylacetate) and tri(trimethylacetate) (0 mil | (methylcyclopentadienyl) zirconium tris(trimethylacetate). In another embodiment of the invention metallocene catalysts containing bulky ligands include those mixed nitrogen-containing cyclic ligands also known as enitrogen catalysts. A transition metal based on two-ischae ligands containing pyridine or cquinoline moieties such as those described in Publications 11 11:

- M. International Patent Applications No. 55/937759 and 94/015481 5 AAJEYTNE and US Patent No. 0.27.7750 are all incorporated into this release for reference. and within the scope of one embodiment of this invention; Compounds 1112 and 7027 can be combined for a metallocene catalyst containing a large ligand described in the © Johnson & Co. articles “New Pd(Il)- and Ni(I)-Based Catalysts for Polymerization of Ethylene and a-Olefins, J.

Am.

Chem.

Soc. 1995, 117, 6414-6415 and Johnson, et al., “Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium(Il) Catalysts”, J.

Am.

Chem.

Soc., 1996, 118, 267-268 and IPP No. XY) 4 of Aug 1 0 14430 which are all incorporated into this release for reference; combined with a carboxylate metal salt for use in the process according to this invention. These Ld complexes may be dialkyl ether additions or either alkylated reaction products of the described dibalide yl complexes that can be activated to a cationic Alla by the use of conventional type cocatalysts or activators according to this invention which Vo will be described below. as well; Metallocene catalysts containing a bulky ligand include those diimine-based ligands of metal compounds of complexes A to 01 described in the two IPOs pursuant to PCT No. 77/0104 AV/EAVYS and Chem. (1998) 849-850.

Comm, pp. © Gibson and AAA who are all incorporated into this release for reference. Metallocene catalysts and other large ligands include those imido complexes of the metals of groups © and “ described in EP 2-0 AV TAS and US 2,851,446 which are incorporated herein for reference. In addition ; The metallocene ve catalysts containing a large ligand include the bis(arylamido) YYW bridge compounds.

-yy - a metal selected from group IV described by D. h. 1.11.1 McConville et al. at 1195, 14, 5478-5480 “Organo-metallics” incorporated into this statement for reference. Other metallocene catalysts containing a bulky ligand as bis(hydroxy aromatic nitrogen ligands) 0 are described in US Patent 2,887,147; which are incorporated into this statement for reference. Other metallocene-type catalysts containing one or more group 10 atoms of the periodic table of the elements include those described in IPO No. 41751/48; which are incorporated into this statement for reference. Other catalysts of the metallocene type that contain a large ligand include those catalysts that are multi-nuclear metallocene and contain a large ligand as described in International Patent Publication No. 44/705785 which is incorporated in this statement for reference. . It is understood that in some embodiments; The bulky ligands of metallocene catalysts according to this invention described above may be Alda disproportionately JBL in terms of additional substituents or types of substituents and/or unbalanced in terms of the number of additional vo-substitutes present on the bulky ligands Or the massive ligands themselves are different. Lad is aware that in one embodiment; Catalysts of the metallocene type containing a large ligand according to the invention include their skeletal, optical, or dissipative structural isomers, meso isomers, racemic, and their mixtures. In another embodiment they may be Compounds of the Y. metallocene type that contain a massive ligand of this invention are anhydrous and/or are a metallocene catalytic compound containing a massive ligand.

“YA - the activator and the activation methods used for the preparation of metallocene catalysts containing a bulky ligand that activate the metallocene catalysts containing day bulky described above according to the invention in several ways For the production of catalytic compounds having a Jee coordination site in which one or more olefins are coordinated, phosphorylated, and polymerized. For the purpose of this description and the accompanying claims; The term 'activator Jade' when used herein means any compound, component or method capable of activating any of the metallocene-type catalysts containing the Ga large ligand of the invention as described above. Such activators may include, for example, For example, but not limited to, Lewis acid, of acid Ve, a non-coordinating ionic activator, or an ionizing activator, or any other compounds including Lewis bases, alkyl aluminums, and conventional co-catalysts. (mentioned earlier in this statement) and combinations thereof can convert a neutral catalytic compound of the type metallocene containing a bulky ligand into a catalytically active cation of the type metallocene containing a bulky ligand. Within the scope of this invention is to use alumoxane ( lus soll or modified alumoxane as an activator; and/or to use ionizing activators as well, whether neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or a semi-metallic precursor of trisperfluorophenylboron, trisperfluoropheny! boron mealloid precursor or semi-metallic precursor of trifluoro. © trisperfluoronaphtyl boron or polyhalogenated heteroborane anions (see International Patent Publication No. 8/4745487) or combination thereof may ionize into a metallocene containing a ligand and in an embodiment of the invention; An activation method is also used that uses ionizing ionic compounds that do not have oe Ye proton Jad but are capable of producing both the catalytic cation of the metallocene type

“ya - metallocene which contains a large ligand as well as a non-coordinating anion has been described in EP 197 4716 1h and 6 Ame OVY and US FAV.

OTA <.0 which has been incorporated into this statement for reference. Various methods for the preparation of alumoxane and modified 0 alumoxane compounds, including but not limited to those described in US Patents Nos. 18, 487.46, 7K, NO, £619 OY, 6/6, and Tech ru “TFCAC, £LATAAYY, FADACH.0, 717, Ficus km, Liam, Ela Lama, :1, 8.41/47, 41.874, Lamkel, 70175679, 2.1.451, 0 0.74.2870, and European Patent Publications Nos. 4796 831 0 HDO OAT 774 .31-6 and YA 44 10m and the International Patent Application Bulletin in accordance with the Patent Cooperation Treaty under the Patent Cooperation Treaty No. (1/46) all of which are fully incorporated into this statement for your reference Ionizing compounds may contain an active proton or some other cation associated with the remaining ion in the ionizing compound, but it is not coordinately bound with it at all, or is bound with it to a small extent (vo) and compounds of this nature and similar ones are described in European publications GAY numbers 4.07/6 Bahm and 444 gA=+ Ove.Alalal 0HGRO 797/7004 and US Patent No. 21570157, 9.148.401, 14761, 197: 9.7, YEY.0X0 .50 9.744. 794 and 9.07.174 ath US Patent Ser. No. 8/788.7850; deposited on 3 ule] 1494 and Ye have all been fully incorporated into this statement for reference. Other stimulants include those described in the International Patent Bulletin pursuant to PCT No. 98/097815 as tris (YY) 1”-nonafluorobiphenyl)fluoroaluminate tris (2, 2, 2”-nonafluorobiphenyl) fluoroaluminate This publication has been fully incorporated into this release for reference.The invention also uses various combinations of activators, for example alumoxanes and ionizing activators in the form of

combined mother See, for example, European Patent 05977175 31 and the two international PCT patent publications Nos. 4/7978 and 44 8/146 and the two US Patents Nos. 5.167.169 and 00467.41.; all of which have been fully incorporated into this statement for reference. be referred to. It describes. International Patent Bulletin No. 094956/18, which was incorporated in this statement to be a reference to refer to the activation of catalytic compounds of the type metallocene containing a large ligand using perchlorates and periodates and iodate 1008168 including their aquatic forms. The ISBNs SAF 10 Y and 0309 4/8/9, which are incorporated herein for reference, describe the use of SL RY CY (phenyl-trimethylsilicate) for lithium (2,2-bisphenyl) 4THF. -ditrimethylsilicate) 01 as an activator of a metallocene catalyst containing a large ligand. Incorporated in this release for reference, ISPM No. 185 describes the use of doping organic boron and aluminum. EP 744 YAY 31-0 describes the use of a silylium salt in combination with a non-coordinating coordinating anion. as well; The invention also uses vo methods, for example, by using radiation (see European patent AY 15+ 31-0 incorporated in this statement to be Electrochemical Oxidation Lampe and the like as activation methods achieving the purposes of making a compound or catalyst precursor of the metallocene type metallocene containing a large neutral ligand or a cation of the type metallocene metallocene containing a large ligand capable of polymerizing olefins described activators or other methods to activate a catalytic compound of the type »> metallocene containing a ligand ded a In US Patents Nos. 0.A04.70Y, 44.07 and 2./24-777 and PCT International Patent Application Bulletin No. 48/77/75; which are incorporated into this statement for reference.

vy - Mixed catalysts Laas It is also within the scope of this invention that catalyst compounds of the metallocene type containing a bulky ligand can be combined with one or more catalyst compounds of formulas (1) and (7) and (©) and (£(5 (0)) using one or more activators or one or more activators and the methods described above. It is recognized in this invention liad that other catalysts can be combined with metallocene catalyst compounds Containing a large ligature according to the invention, see for example US Patents Nos. 4,477,749, 4,478,494, 8,781,374, 05, 7/..8011.H, 0.714.741, which are all fully incorporated into this - the statement for reference. In another embodiment of the invention, one or more metallocene catalytic compounds or systems containing a bulky ligand may be used in combination with one or more conventional catalytic compounds or systems. Mixed catalysts and mixed catalyst systems in US Patents Nos. 1446, Lakhta, 017, ye Lam and Malala 4 OVAYLATY, OFAN., 0.8810, © 4764, 0.777.944, 0.7397..71 and IPO pursuant to PCT No. 96/770010 issued on August 1, 14576 All these publications have been incorporated into this statement in full for your reference. It is also recognized that two or more transition metal catalysts of the conventional type can be combined with one or more co-catalysts of the conventional type. Conventional alloyed transition metal catalysts are described, but not limited to, in US Patents Nos. 421840, ¥1..004.£, 71477, Lect-At, 8a, 16 8.1, 0.737/..76, 0.4.16, and 2.470. .040 which are all incorporated into this statement as Les se is referred to.

Compounds and systems of a metallocene catalyst containing a large ligand and compounds and systems of a conventional transition metal catalyst can be combined with one or more supports or carriers or carriers using one of the known catalyst loading methods 0 is good at technical or as will be described below. In a preferred embodiment; The method of the present invention utilizes a polymerization catalyst in a portable form. For example, in the most preferred embodiment, the catalyst or catalytic system is of the metallocene type containing a bulky ligand in eg portable form deposited on, in contact with, or embedded in an adsorbent or adsorbent support or dala. The terms “support” or “carrier” when used interchangeably in this statement mean any support material that is porous or non-porous and preferably a supportive material that is porous, for example talc, inorganic oxides and inorganic chlorides. These include Other carriers Jie polystyrene resin supports, functional or cross-linked organic supports Jie polystyrene, divinyl benzene, polyolefins, polymeric compounds or any organic support material The preferred carriers are inorganic oxides including those metal oxides of groups (¥), (©), (4), (0), (VF) or (VE) from the periodic table of elements. Preferred supports include silica, alumina, silica-alumina, magnesium chloride and mixtures thereof. Other useful supports include magnesia and titania titania, zirconia, montmorillonite, etc. Also, combinations of these supporting materials can be used, for example, silica-chromium and silica-titania. For the carrier, which prefers to be an inorganic oxide; Yo surface area in gad from about 01 to about 701 m'/g and pore space

Cy - volume : 0 m in the range from about 010 to about ; cm/g and an average particle size in the range from about 01 to about ©0000 µm. the best; The surface area of the carrier ranges from about 90 to about 0001 m"/g and its pore space ranges from about 1# to about anf pu Yeo and its average particle size ranges from about 0 to about Yee 000 µm. It is more desirable that the surface area of the carrier ranges from about 100 to about 5080 m/g/m and its pore space ranges from about 1.8 to about ?cm/g and its average particle size from about 01 to Usually the average pore size of the carrier according to the invention ranges from about 01 angstroms to 0 ang and preferably from 00 angstroms to about 0000 ang and most preferably Vo ey to about You Examples of carrying metallocene catalyst systems containing bulky Alay according to the invention are described in US Patents Nos. 4,701,477, 4,008,911, 176, 1M47, 47717, Laney, OYFAALY, and 4 Wy Clam 6.¥E1.4Y0, 417.76, 44 Tata, D0 2/11, 37m, 0.604.910, 886/4, 8.174.707, Mi14m, 0.1Y0.0 V0, Anah, 0.110.110 5 Malcollate, 64, 4:30 7v, 407 a/at, 271711, 8.84.446, 717..7.©, 0.770.574, US Patent Application Serial No. 771.998 Filed July 1, 1944, Serial No. 78.7771 Filed at YY January 1999 © Gay International Patents PCT Applications and Publications Nos. 45/774406, 16/146044, 2/5897 and 97/077997 are all fully incorporated into this release for reference. Examples of carrying catalyst systems of a conventional type according to the invention are described in US Patents Nos. 4,444,474, 4.7/37, 1,748.704, 764 4.07/4, 5438.496, VOA vo £080, 2..7.854; All of which are incorporated into this release for reference.

It should be recognized that metallocene catalyst compounds containing a bulky ligand according to the invention may be deposited on identical or separate supports with an activator or the activator may be used in unmounted form or may be deposited on a support different from the metallocene catalyst compounds containing a large portable ligature a, of the invention or 0 any combination thereof. There are various other methods in the technique of carrying a polymerization catalyst compound or system according to the invention. for example; The metallocene-type catalyst containing a bulky ligand according to the invention may contain a polymer-bound ligand as described in US Patents 5,477,707 and 2,797,755 which are incorporated herein in full by reference 0; The metallocene catalyst system containing a bulky ligand according to the invention may be spray dried as described in US Patent 15.248.71, which is fully incorporated herein for reference; The carrier used with the metallocene catalyst system containing a large ligand La cpl iad contains functional groups as described in EN 707 807 AT 16. Fully incorporated herein for reference; or choose an alternative or easily removable assembly as described in US Patent No. 688.8850.©; which are incorporated into this statement in full for reference. In a preferred embodiment; The present invention presents a portable metallocene catalyst system containing a bulk ligand incorporating a surfactant used in the preparation of the portable catalyst© system; As described in the International Bulletin pursuant to the PCT No. 1/174 which is incorporated into this statement in full for reference. A preferred method for producing a portable metallocene catalyst system containing a bulk ligand of the invention is described below and can be found in US Patent Applications Serial No. 7765.077 filed YE June 1944 and Serial No. 115.097 filed in TE June 1944 and my publication The two international patents according to the cooperation treaty

“yo - in the field of patents Nos. aT/0eY Eo and TE 35/0; Issued £8 Jan E5099 are all fully incorporated into this statement for reference. And in this preferred way; £35 The metallocene catalyst compound which contains a large ligand in a liquid to form a metallocene solution and a separate solution containing an activator 0 and a liquid is formed. The liquid may be a compatible solvent or any other liquid capable of forming a solution or the like with catalyst compounds of the metallocene type containing a bulky ligand and/or the activator according to the invention. and in the most favorable embodiment; The liquid is an aliphatic or aromatic hydrocarbon, and the most preferred is toluene, and the two solutions of the catalyst compound of the type metallocene, which contains a huge ligand 1 and the activator, are mixed together and added to a porous support or the porous support is added to them so that the pore space The total solution of the metallocene catalyst compound that contains a bulky ligand, as well as the activator solution or the metallocene catalyst compound that contains a bulky ligand and the activator is less than five times the pore space of the porous carrier, and the best is less than four times, and the best is BU Less than three times. Provided that the preferred ranges range from 011 to ©. © once, and the most preferred ranges from 017 to ? times. Procedures for measuring the total pore space of a porous support are defined in the technique. One such procedure is detailed in Experimental Methods in Catalytic Research (Academic Press 141A vol.0; specifically, pp. 47-717. This preferred procedure includes the use of tv. Conventional Nitrogen Adsorber 0100860 according to the method of Bronnar, Emmett and Teller Another well-known method in the technique is described in the article “Total Porosity and Particle Density of Catalyst Fluids by Liquid Calibration” by “Fluid Catalysts” Liquid Titration in the name of cInnes YA volume ? in a book entitled cAnalytical Chemistry p. cule (7 4-7717 1407)

The molar ratio of the metal of the activated component to the metal of the catalyst compounds of the metallocene type, which contains a large ligand, ranges from 0:0. To .1:5080 and when the activator is an ionizing activator Jia those based on the quaternary anion (pentafluorophenyl) boron ctetrakis(pentafluorophenyl)boron ° and it is preferable that the molar ratio of the activated component metal to the catalyst metal component ranges from 0:01. to ?:0. In one embodiment of the invention; One or more olefins polymerize; Preferably one or more alpha-olefin containing of ? to Ye a carbon atom and preferably ethylene or propylene or their terminator combinations in the presence of a metallocene type 0 catalyst system containing a bulk ligand and/or transition metal catalysts of a conventional type according to the invention prior to polymerization the basic. Prepolymerization can be carried out in a discontinuous or continuous manner in a gas phase, solution or slurry and under elevated pressures. The prepolymerization may be carried out using any olefin monomer or combination and/or in the presence of any molecular weight control agent Jie hydrogen. For examples of prepolymerization procedures; US 0 Patents Pending Nos: 8.771, MATCLA, 4777, 4714876, 187.7©, 0.V 1 0.0VA, European Patent Publication Ame 774 ATY, International Patent Publication PCT No. 57 /46971; All of which are incorporated into this statement fully for reference. The prepolymerized catalyst system to fulfill this description and the appended safeguards is a portable catalyst system. vy. carboxylate metal salt Hil carboxylate metal salts all have been well known in the technology as additives used with polyolefins eg as a film curing aid. These types of post-treatment additives are usually used in the reactor as emulsifying agents, antistats, all antifogging agents +0, stabilizers, foaming aids, and lubricating agents.

“yy - lubrication aids, mold release agents, nucleating agents, Jal se 5 agents, slip agents, anti-blocking agents, and the like. Thus it was not anticipated by Sad that these upstream reactor auxiliaries or agents would be useful with a polymerization catalyst to improve the operability of the polymerization process. For the purpose of this description and the accompanying claims; The term “carboxylate metal salt” when used in this statement means the salt of a mono-, di- or tri-carboxylic acid with a metallic element from the periodic table of elements . Examples include, but are not limited to, 0 saturated, unsaturated, aliphatic, aromatic, or cyclocarboxylic acid salts; Where preferably ligand 01 contains a carboxylate of ? to YE a carbon atom such as acetate, propionate, butyrate, valerate, pivalate, caproate, isobuytlacetate <A, t-butyl acetate acetate, caprylate, heptanate, undecanoate <4 sia pelargonate, oleate, octoate, palmitate, myristate, margarate Vo, stearate, arachate, turcosanoate, Jad y .tercosanoate Examples of the metal element, for example, are not limited to a metal from the periodic table of the elements to choose from the category consisting of Al 5 p118, 08, Sn 5Sr 11, Alo 38, 270, sMn sHg sCd sFe 00, and Na sLi Pd. sNi and in embodiment; The carboxylate metal salt is represented by the general formula vy. M(Q)x(OOCR)y where M is 136 choices from groups 1 to 11 of the lanthanide series and actinide, preferably from groups 1 to 1 and 1 to 11, and the best from groups © to V and 1 to 01, and the most preferred groups 1 and 1” and the best (WU) Group Qs VY Jig vo halogen or hydrogen or hydroxy or hydroxide

“YA - HYDROXIDE OR aryloxy alkoxy group or siloxy or silane or sulfones 501/00816; Jia Rg hydrocarbyl cleft It contains who? to 100 carbon atoms, preferably; to +0 x5 carbon fae is an integer from zero to an integer from 1 to ; So that 0 is the sum of and l is equal to the valency of the metal. In a preferred embodiment of the above formula ote y is an integer ranging from 1 to ¥ and preferably from 1 to 1 especially when 14 represents a metal of group AY and the examples of group © in the above formula for example do not The mats contain hydrocarbyl moieties. to 100 carbon atoms including 0-alkyl moieties, aryl, saturated or unsaturated aromatic, aliphatic, or cyclic hydrocarbyls. In one embodiment of the invention; Jig R is a hydrocarbyl moiety containing A or more carbon atoms, preferably VY is a carbon atom or more, and the best is 17 carbon atoms or more. In another embodiment; R represents a hydrocarbyl moiety containing from 11 to 90 carbon atoms, preferably from 17 to VY carbon atoms, and most preferably ve from 117 to 4© atoms Examples of © in the above formula include, but are not limited to, a group containing one or more similar or different hydrocarbons such as an alkyl, cycloalkyl, aryl, or alkynyl alkenyl or arylalkyl or arylalkenyl or alkyl aryl or alkylsilane or arylsilane Y. or alkylamine or arylamine or alkyl An alkoxy alkyl phosphide or alkoxy contains from 1 to 70 carbon atoms and the hydrocarbon-containing group may be linear or branched or even carry substituents. as well; Ji 0 may in one embodiment be an inorganic group Jie halide, sulfate, or phosphate.

- »m and in the embodiment; The most preferred carboxylate metal salts include aluminum carboxylates such as Jie, aluminum stearates, octoates, oleates, and cyclohexylbutyrates. A more preferred embodiment of the carboxylate metal salt Hall salt could also be “(CH3(CH)16CO0)3Al i.e. aluminum tri-stearate (preferred melting point is 111 pA). (CH3(CH,)6CO0),Al-OH i.e. aluminum di-stearate (preferred melting point £0 Y dm) 5 “CH3(CH,)16CO0-AI) OH), mono-stearate (preferred melting point is 198 dM).Ve includes but is not limited to commercially available carboxylate metal salts and Witco Aluminum Stearate No. Aluminum Stearate # 18 YA, Witco Aluminum Stearate # 22 YY, Witco Aluminum Stearate # 117 #132, Witco Aluminum Stearate EA Food Grade, all supplied by Witco Corporation, Memphis, Inc. In one embodiment; The melting point of the carboxylate metal salt ranges from about 0 dm to about 5*0 dm and the best is from about 71? dm to about 7710 dm and the most preferred is from about 0 dm to about 0 dm to About ‎You Med and best of all from about ‎100 Med to about ‎Yoo Med and in the most favorable embodiment; The carboxylate metal salt Hall salt is an aluminum stearate with a melting point ranging from about 15 dm to about 119 dm. In another preferred embodiment, the melting point of the carboxylate metal is higher than the polymerization temperature in the reactor. Other carboxylate metal salts include titanium stearates, tin stearates, and calcium stearates.

85, zine stearates, boron stearate, and strontium stearates. In one embodiment; The carboxylate metal salt can be combined with anti-electrostatic agents, Jie, fatty amines, for example, adding M-zinc Kemamine 990/2 Kemamine AS 990/2 zinc AS, which is a combination of stearyl ethylamine ethoxylated stearyl amine and zinc stearate, or chemamine 999/3 Kemamine AS 990/3 AS, which is ethoxylated stearyl amine, zinc stearate, and octadecyl-H SGT -th- Butyl--hydroxyhydrate and octadecyl-3,5-di-tert-butyl-4-cinnamate

Witco 0 216 blocks 170+0<77700. Both of these blends are available from Witco Corporation | 0 Memphis, Tenn. “Corporation Method for preparing the catalyst composition The method for making the catalyst composition generally involves the incorporation, contact, and/or synthesis of dfs. Mixing of a catalyst system or catalyst polymerization with a carboxylate metal salt b and in. One embodiment of the method according to the invention; combines and/or comes into contact with dfs synthesizes and/or blends a transition metal catalyst of a conventional type and/or a metallocene catalyst containing a bulky ligand with at least one carboxylate metal salt - and in the most preferred embodiment ; The transition metal catalyst is of the conventional type and/or a metallocene catalyst containing a bulky ligand carried on a support material. Ye and in the embodiment of Jedd AT the steps of the method of this invention the formation of a polymerization catalyst and preferably the formation of a portable polymerization catalyst and the contact of the polymerization catalyst with at least one carboxylate metal salt 0 and in a preferred method; The polymerization catalyst includes a catalyst, an activator or a co-catalyst, and a carrier, preferably a metallocene-type mobile catalyst containing a bulky ligand. Bad hurt

-+1 - A master of the technique understands that certain conditions of temperature and pressure need to be applied to avoid, for example, the loss of effectiveness of the “Glial” system depending on the catalyst system and the carboxylate metal salt lll. In one embodiment of the method of the invention; The carboxylate metal salt 0 comes into contact with the catalyst system, and a portable catalyst system is preferred. Most preferably, a portable catalytic system of the type metallocene, which contains a large ligand at ambient temperatures and pressures. The contact temperature used to combine the polymerization catalyst and the carboxylate metal salt preferably ranges from zero Celsius to about 100 dC, preferably from 10 dC to about Vo dC, and most preferably at about a temperature 0 and ambient atmospheric pressure. : : and in a preferred embodiment; The polymerization catalyst and the carboxylate metal salt come into contact in an inert gaseous medium, Jie nitrogen. more, solvents and hydrogen ‎hydrogen | 0 and the like. In one embodiment; (Say) addition of a carboxylate metal salt in 4 stages during the preparation of the polymerization catalyst. In one embodiment of the method of the invention, the polymerization catalyst and the carboxylate metal salt are combined in the presence of a liquid eg which may be mineral oil Mineral oil 01, toluene, hexane, isobutane, or Lee's mixture, and in a more preferable way, the carboxylate metal salt is combined with a polymerization catalyst that may be formed in a liquid, preferably in a ridge or Combined with a dried or substantially dried polymerization catalyst that has been placed in a liquid and foamed.In an embodiment, the contact time between the carboxylate metal salt 0 and the polymerization catalyst may vary depending on one or more conditions and the temperature

ey - Pressure, type of mixing device, quantities of components to be combined, as well as the mechanism for adding the polymerization catalyst and carboxylate metal salt combination to the reactor. preferably in contact with the polymerization catalyst; which is preferably a metallocene catalytic compound containing a bulky ligand and a carrier; In contact with the carboxylate metal salt 0 for a period of time ranging from about a second to about YE an hour, preferably from about one minute to about 11 hours, and the best is from about 10 minutes to about 10 hours, and most preferably From about Te minutes to about A hours. and in embodiment; The weight ratio of the carboxylate metal salt to the weight of the transition metal of the catalyst compound ranges from about 0000 to about 0001, preferably from 1 to about 001, preferably from about 7 to about 00, and most preferably from ; to about .01 and in one embodiment; The weight ratio of the carboxylate metal salt to the transition metal weight of the catalyst compound ranges from about ? To about Yo and preferably from about ? to about 11 and better than ; to about .01 and in another embodiment of the method of invention; The weight percentage of the Vo carboxylate metal salt on the basis of the total weight of the polymerization catalyst ranges from about 0.5 by weight to about 5080 by weight and preferably from about 7 by weight to about 785 by weight and preferably from about 77 by weight to about IVY by weight and more in preference from about 77 wt. to about 70 wt. In another embodiment; The percentage by weight of the carboxylate metal salt | based on the total weight of the polymerization catalyst ranges from 1 to about 0 75 wt©, preferably from 77 by weight to about 770 by weight, most preferably from about 7" by weight to about 7710 by weight. In one embodiment, when the process of this invention produces a polymeric product having a density greater than 71 g/cm"; The total weight percentage of the Sil carboxylate metal salt based on the total weight of the polymerization catalyst is greater than 71 by weight. and in another and vo as well; When the process produces a polymeric product with a density of less than 0051g/cm, it is

- © Total weight percentage of the carboxylate metal salt Jl based on the total weight of the polymerization catalyst Jef of 77 by weight. If the polymerization catalyst includes lla sale, the weight of the support material is within the total weight of the polymerization catalyst. It is believed that the higher the metal content in the activator; For example, the aluminum content ° or the free aluminum content (the alkyl aluminum content in the o(alumoxane) compound in the polymerization catalyst; the greater the carboxylate metal salt is required. The treatment of the amounts or payloads of the polymerization catalyst components, i.e., free aluminum, provides a means for adjusting the level of the carboxylate metal salt all Ve. The mixing techniques and equipment that may be used in the method of the invention are well known. Any of the means of mechanical mixing eg shaking, stirring, barrel stirring and rolling Other techniques include the use of anal eg in a Cus fluidized bed reactor vessel Mixing is achieved by circulating gases The mill includes mixing equipment used for amalgamation According to the most embodiment Solid polymerization catalyst and 1 solid carboxylate metal salt to name but a few Ribbon blender, electrostatic mixer, double cone blender and drum tumbler a drum roller, a dehydrator, a fluidized bed, a helical mixer, and a conical screw mixer r. In embodying the method of the invention; al A transition metal catalyst of the traditional portable type, preferably a portable catalyst of the metallocene type containing a large ligand; With a carboxylate metal salt for a period of time sufficient for a significant portion of the portable catalyst to mix thoroughly and/or come into substantial contact with the carboxylate metal salt.

In a preferred embodiment of the invention; A catalyst system according to the invention is mounted on a carrier preferably a portable catalyst system that is essentially dried, preformed and/or essentially dried df smooth flow. and in a particularly preferred way ly of the invention; The preformed mobile catalyst system is immersed with at least one carboxylate metal salt. And the metal carboxylate salt Li 3 carboxylate metal salt is in solution or in a ridge or in a dry state and it is preferable that the Lila carboxylate metal salt be substantial or in a dehydrated Alla. and in the most favorable embodiment; The carboxylate metal salt comes into contact with a portable catalyst system, preferably a metallocene portable catalyst system containing a bulky ligand in a rotating mixer under nitrogen atmosphere 0 | It is absolutely preferable that the mixer be a “tumble mixer SE” or in a fluidized bed mixing process; where the polymerization catalyst and the carboxylate metal salt in Alls are solid; That is, both in Ala are essentially dry or dehydrated.

In the embodiment of the method of invention; A transition metal catalyst of a conventional type 1 contacts and a metallocene catalyst containing a bulky ligand is preferred; with Jala to form a portable catalyst complex. And in this way; An activator or co-catalyst of a catalyst compound contacts a separate carrier to form a portable activator or a mobile co-catalyst. It is understood that in this particular embodiment of the invention; The carboxylate metal salt is subsequently mixed with the portable catalyst, portable activator, or portable cocatalyst; in any particular order ©” or mixed separately or simultaneously mixed or mixed with only one of the catalysts carried or preferably with the activator carried before being mixed with the catalyst and activator or co-catalyst carried in

separate image. As a result of using a combination of the polymerization catalyst and Sil carboxylate metal salt according to the invention; The overall flow of catalyst into the reactor should be optimized. ve and despite the fact that the said catalyst flux is not as good as the salt-free catalyst

- 0 metal carboxylate (carboxylate metal salt), the flowability of the catalyst and tas carboxylate combination of the invention is no longer a problem. feeder brushes, feeder pressure purges from the feeder, and the like o In the OAT embodiment the polymerization catalyst and the carboxylate metal salt may come into contact with a liquid; Jia mineral oil and the product is added to the polymerization process in a fluidized state. And in this particular embodiment; Preferably as a polymerization catalyst, pana and in some polymerization processes; It is preferable to use carriers with a smaller particle size. However, the operability of these processes is considered intractable. It was discovered that when using a combination of the polymerization catalyst 0 and the carboxylate salt Hall of the invention; Deel materials with a smaller particle size may be successfully used. for example; Silica can be used with an average particle size of about 10 microns to Ar microns. Silica 8 materials in this size are available from Crosfield Limited Warrington; of alas) eg Crosfield 88-70 128-70 Crosfield with an average particle size of YO to . 56 microns. unwilling to adhere to any particular theory; It is usually believed that the use of support materials with a smaller average particle size produces finer particles and this results in the catalyst being subjected to additional lamination. It is also believed that the use of a metal carboxylate with the polymerization catalyst ensures better particle growth during polymerization. This fine particle morphology is believed to result in the formation of Ji particles and a lower susceptibility to lamination. Thus the use of ¥ carboxylate allows the use of a support material with a smaller particle size. and in embodiment; The method of the invention provides that a non-carrying polymerization catalyst and a carboxylate metal salt are co-injected into the reactor. In one embodiment; The polymerization catalyst is used in an unmounted form; Preferably in liquid form as described in detail in US Patents 8,717,077 and 5,147,777 and EP OAT WAY 2.-vo - all of which are incorporated herein for reference. Polymerization catalyst can be fed in

liquid form with a carboxylate metal salt into a reactor using the injection methods described in the International Patent Publication pursuant to PCT No. 4 which is fully incorporated into this release for reference. When using a combination of a carboxylate metal salt and a 0 portable metallocene catalyst system containing a large ligand; The molar ratio of the metal of the activation component to the metal of the metallocene catalyst complex which contains a large ligand ranges from 0:0.” to 0 . 00 preferably from 0:001 to eee and most preferably from 0:090:1 to 1:7001. Polymerization Process 1 The catalysts and catalyst systems according to the invention described above are suitable for use in any polymerization process. Polymerization processes include a process in solution, gas phase or slurry phase at high pressure or a combination thereof and a particularly preferred process is the polymerization in gas phase or slurry phase of one or more olefins of which at least one is ethylene or propylene .propylene 1s and in one embodiment; The process of this invention is directed toward the polymerization process in a solution, sludge phase, or gas phase of one or more olefin monomers containing from *1 AY a carbon atom, preferably from 7 to a VY carbon atom, and the best is ? Lila is particularly suitable for the polymerization of two or more monomers of olefins comprising ethylene, propylene, 1-butene-1 Y, and 1-pentene. pentene-1 and 4-methyl-1-pentene 4-methyl-1-pentene and 1-hexene-1 and 1-octene-1 and 1-decene .decene-1 Other monomers useful in the process of the invention include unsaturated ethylene monomers, ASE olefins containing from 4 to YA carbon, exchangeable or unchanged 1068L dienes, polypairs, and ve vinyl monomers. and cyclic olefins. Examples of monomers useful in this invention include eg

-gy - for example, but not limited to norbomene, norbomadiene, isobutylene, vinylbenzocyclobutane, styrenes, and styrene containing an alkyl substitute, ethylidene norbomene, and isoprene isoprene and dicyclopentadiene and pentene .cyclopentene Als : In the most favorable embodiment of the process of the invention; It produces a copolymer of ethylene Cua cethylene copolymerizing a monomer containing at least one alpha-olefin having of ; to 11 carbon atoms, preferably from; to VY a carbon atom and most preferably of ; to / carbon atoms «htth; with ethylene in a gas-phase process. In another embodiment of the invention process; ethylene or propylene 0 polymerizes with at least two different co-monomers; One of them may be the diene to form a ternary polymer. In one embodiment; directs the invention towards a process; especially a process in a gaseous phase or reductive phase; For the polymerization of propylene alone or with one or more monomers including ethylene and olefins containing of ; to VY carbon atom 8:000. Sixteen propylene polymers may be produced using particularly bridging catalysts of the metallocene type containing a bulky ligand as described in US Patents Nos. 0.795.476 and 2.778.7764.; which are incorporated into this statement for reference. usually; In the gas-phase polymerization process, a continuous cycle is used, where in one part of the cycle of the celia system a circulating gaseous stream, also called a recirculating stream or a dilute medium, is heated in 0 | reactor by heat generated from the polymerization process. This heat is removed from the recycled composition in another part of the cycle by a cooling system located outside the reactor. clases A gaseous stream containing one or more monomers circulates continuously in a gaseous fluidized bed process used to produce polymers; through a fluidized bed in the presence of a catalyst exposed to the reacting conditions. The gaseous stream is withdrawn from the fluidized bed and recycled to the reactor. at the same time vo; The polymer product was withdrawn from the reactor and a new monomer was added to replace the polymerized monomer

M - (See eg US Patents Nos. 4,847,744, 5,88,746, YAY.0, “I, 087/494, 0.£40,4YY,” 241:14, 8,467,491, 8.457 .444, 8.213.351, and .0TTALYYA (all of which are fully incorporated into this release for reference).

° The reactor pressure in the gas-phase process may vary from about 100 psi' (140 kPa) to about 5000 psi' (YEA) kPa) and is preferably in the range of about 100 psi TVA (TVA) to about 00 YVod) Tia sy dh kilo (July) and best in the range from about 100 lbs/in” E (177 kPa) to about You pounds per inch" (404.7 kPa).

1 The temperature of the reactor in the gas-phase process may vary from about F d C to

| About 11 dm, preferably from about 01 dm to about 111 dm, and the best from about 1 dm to 0 dm, and the most preferable from about 71 dm to about 2390 Other gas-phase processes according to the process of this invention include those described in US Patents Nos. 8,577,747 and 8,268,818 and SLTVYLTYVE and European Patent Publications ae Nos. Yeu 44 for YoY A= KN and 4 L 0 2e and TYE 471-5 which are all incorporated into this release in full for reference. In a preferred embodiment; The reactor used in this invention can by the process of this invention; zl) over 5000 lbs of polymer per hour (YTV (kg/hr) to about You os lbs/hr (0 900 kg/hr) or more preferably over 0001 lbs/hr) © (£00 kg/hr) or better than 00001 lb/hr (540©; kg/hr) or better than Youu lb/hr (VIF (kg/hr) or better than 19 lbs/hr (19,900 kg/hr) or better than Seine lb/hr (77,700 kg/hr) and most preferably over 150,800 lb/hr (Yau (kg/hr) to over 000001 lbs/hr (£0,000 kg/hr).

B"

The polymerization process in the sludge phase generally uses pressures in the range from about 1 to about 50 atm and even higher and temperatures in the range from zero degrees Celsius to about 171 dm. In the al-phase process, a suspension of solid particulate polymer is formed in a liquid diluent medium for polymerization, Gus. Ethylene, co-monomers, and We hydrogens are added with the catalyst. The suspension comprising the diluent is removed from the reactor intermittently or continuously as the volatile components are separated from the polymer and recycled, possibly after distillation, into the reactor. Usually, the liquid diluent used in the polymerization medium is an alkane containing from “to 1” carbon atoms, and the medium used should be liquid under polymerization conditions and relatively inert. When a propane medium is used, the process should be operated at a temperature and pressure above the critical value of the reactant. Preferably

Using Jaws of hexane or isobutane .isobutane The preferred polymerization technique according to the invention is called particle polymerization or the ridge process; The temperature is kept at a lower value than the temperature at which the polymer turns into solution. This technique is well known in the technique and described for example in the US patent vo FLY EAN YA which is fully incorporated into this statement for reference. Other redig processes include those using a loop reactor and those using a combination of stirred reactors in series or parallel or combinations thereof. Examples of redig processes include but are not limited to continuous loop or stirred tank processes. Other examples of redig processes are also described in US Patent 4,717,484 which are fully incorporated into this

- Statement for reference for reference. and in embodiment; The reactor used in the quenching process according to the invention can by means of the process of this invention; Produce over 70,000 lbs of polymer per hour (9,017 kg/hr), preferably over 508,000 lbs/hr (77,714 kg/hr), and most preferably over 0 lb/hr (080 kg/hr) . In another embodiment the sludge reactor in the vo process of the invention produces in excess of 050,000 pounds of polymer per hour (180 lb/hr) and preferably

Coe - over 790,060 lb/hr (YE) kg/hr) to approximately 000001 lb/hr (00 kg/hr). Examples of solution processes are described in US Patent Nos. 4,771.058, 8..01.706, 0.77.544, and 0.004.005 which are fully incorporated into this statement 0e for reference. The preferred process of the invention lies in a process preferably in a slurry or gas phase operating in the presence of a metallocene catalyst system containing a bulky ligand and in the absence or essentially free of any scavengers such as triethylaluminum chloride and triethylaluminum chloride. Jie aluminum trimethylaluminum tri-isobutyl ye aluminum tri-isobutylaluminum tri-n-hexylaluminum tri-n-hexylaluminum diethyl aluminum dibutyl zinc and the like . This preferred process is described in the International Patent Bulletin pursuant to PCT No. A0Y 45/0 and US Patents Nos. 5,717,387 and 2,717,547 which are incorporated into this statement for reference (Legal) for reference. However, it was discovered that Jai had implemented a polymerization process employing a combination of 1. of the catalyst system and the carboxylate metal salt according to the invention using a small amount of a scavenger with little or no effect on process workability and catalyst performance. Thus the present invention presents in one embodiment a process for the polymerization of one or more olefins in a reactor with a metallocene catalyst system containing a bulk ligand, a metal carboxylate salt 08:10(1816) and a scavenger. In an embodiment; the yield of the polymerization catalyst and/or the catalyst composition representing the polymerization catalyst and the carboxylate metal salt is greater than 1,500 g of polymer per g of catalyst and preferably in excess of 10,000 g of polymer per g of catalyst It is best that you exceed 000g of polymer per gram of catalyst and most preferably more than 000g of polymer per gram of catalyst.

01 - In the OAT embodiment, the yield of the polymerization catalyst and/or the catalyst composition representing the polymerization catalyst and the carboxylate metal salt is greater than 0001 g of polymer per g of catalyst, preferably more than 70 080 g of polymer per gram of catalyst and preferably in excess of 40000g of polymer per gram of catalyst and most preferably in excess of 5000g of 0 polymer per gram of catalyst. In one embodiment; The polymerization and/or synthesis catalyst has a reactivity ratio usually less than Y and most commonly less than 1. The reactivity ratio is defined as the molar ratio of a co-monomer to the monomer entering the reactor as measured for example in the gaseous composition of the gas phase process; Divided by the molar ratio of the co-monomer to the monomer present in the polymeric product 0 to be produced. In a preferred embodiment; reactivity is less than 0076, preferably less than 14, most preferably less than 1-7, and in the most preferred embodiment; The monomer is ethylene and the co-monomer is an olefin containing ? One or more carbon atoms, and the best is alpha-olefin, containing; One or more carbon atoms and most preferably an alpha-olefin chosen from the class consisting of 1-vo butane-1 and 4-methyl-1-pentene 4-methyl-1- pentene and 1-pentene©01086-1m and 1-hexene-1 and 1-actene .octene-1

and in the AT embodiment of the invention; When moving from a first polymerization catalyst to a polymerization catalyst (obs), it is preferable where the first and second polymerization catalysts are a metallocene catalyst compound that contains a bulky ligand, and the best where the second polymerization catalyst is a bridge catalyst compound of Metallocene type contains a huge ligand; it is preferable during the transition to use a catalytic composition of carboxylate metal salt

Incorporated with a metallocene bridge catalyst containing a large ligand. And when the ch pall process starts, especially the gas phase process. There is a high susceptibility to operability problems. Thus, in this invention it is desirable to use a mixture of vo polymerization catalyst and a carboxylate metal salt at startup to reduce or eliminate

startup problems. In addition to that; It is also understood that once a reactor is operating and in a steady state; A transition step to the same or different polymerization catalyst can be performed without the presence of the carboxylate metal salt. In the Play AT embodiment, an inactivated or near-inactivation polymerization; 0 should transition to a mixture of a polymerization catalyst and a carboxylate metal salt according to the invention. It is believed that this transition between the polymerization catalysts causes Laie to increase workability problems. Evidence of operability problems has been known in the technology. Some of these indications in the gas phase process include temperature deviations in the reactor, sudden changes in pressure, excessive static generation, unusually static dle sparks, 0 Ah cuts, plating, and the like. and in embodiment; A carboxylate metal salt may be added to the reactor directly, especially when workability problems increase. It was also discovered that by using a polymerization catalyst combined with a carboxylate metal salt according to the invention, it facilitates the production of high-density polymers with a fractional melt index. In one embodiment; The invention provides a process for the polymerization of one or more olefins in 1 reactor in the presence of a polymerization catalyst combined with a carboxylate metal salt to produce a polymeric product having a melt index of less than about 1 dg/min and a density of more than 0 .17 g/cm' and the best is a polymeric product with a melt index of less than about 175 dg/min and a density of more than 1975 g/cm. The polymerization catalyst used is preferably a metallocene catalyst containing a bulky ligand and preferably the process is a gas-phase process and the polymerization lis includes a carrier. It should be understood that by using a combination of a polymerization catalyst and a carboxylate metal salt according to the invention; Transitioning to one of the more difficult-to-produce polymer varieties will be easier. Thus, in one embodiment; The invention is directed towards a process for the polymerization of one or more olefins in the presence of a first catalytic composition under stable conditions preferably vo under egal-phase process conditions to produce a first polymeric product. And have the first polymeric product

“ov - density of more than 0187 g/cm’ and a magma index of more than 14 g/cm (preferably more than af an”.9) and a magma index in the range from 1 dg/min to About 001 decigram/minute, and preferably more than 1 decigram/minute, to about 001 decigram/minute, and it is better to be more than 1 decigram/minute, to about 50 decigram/minute, and the most preferred is 0 Exceeding from 1 dg/min to about 01 dg/min. This process also includes the transition step to the synthesis of a second catalyst to produce a second polymeric product having an AES of more than AY g/cm, preferably more than 15705 g/cm, and a melt index of less than 1 dg/min, preferably less than 0.78 dg/min.The second catalyst composition comprises in combination a conventional transition metal catalyst and/or a metallocene catalyst containing a bulk 0 ligand and a carboxylate metal salt and within The scope of this particular embodiment also is that the transition from a first polymeric product having a T/T value (as described below) less than YO to a second polymeric product having an I/D value greater than YO and preferably greater than Ye and better yet than Yo Z and in the AT embodiment as well; Jad The process of this invention alternates between the use of a first Vo catalyst composition comprising a mixture of a first polymerization catalyst and a carboxylate metal salt And a catalyst composition of a second polymerization catalyst devoid of carboxylate metal salt to improve ALE overall operation of the process. to the reactor separately. and in any of these embodiments; The polymerization catalysts I and II are identical or different. The polymeric product according to this invention The polymers produced by the process of this invention can be used in a wide variety of products and end use applications. The polymers resulting from the process of this invention include linear low-density polyethylene, elastomer polymers, and elastomer polymers.

Cos - and high-density polyethylene and low-density polyethylene and polypropylene pad sill polypropylene contribution from polypropylene .polypropylene and be for polymers; Any Gale ethylene based polymers Density in the range from g/cm' to Tefen 17 preferably in the range from AA g/cm' to Tafa 1.476 6 and even better in the range of 19080 g /cm'' to 97g/cm'' and better yet in the range from 1906g/cm' to 9©6.0g/cm' and even better in the range from CAV g/cm? to 194 g/cm” and the most preferred is more than 0915 g/cm” and preferably more than 197 g/cm” and the absolute best is more than 0.978 g/cm”. This invention has a molecular weight distribution of 0 and the ratio of a mean molecular weight to a numerical mean molecular weight (MoM) of more than 2 to about 11 and in particular ranges from higher than AY about 01 and preferably ranges from more than about YY to as little as about + and more preferably from Yo to 8. The ratio of −14.04 can be measured by gel transmission techniques well known in the technique. Composition Distribution Breadth Index (CDBI). in VA Feb 17 which are fully incorporated into this release for reference.Ye In an embodiment the metallocene catalyzed polymers containing bulk ligand according to the invention have values of 0011 typically ranging from more than 0 75 to 739, preferably 05 to 785, preferably from 710 to TAY, preferably more than 7160, and preferably more than 0. In the AT embodiment, polymers produced by conventional transition metal catalysts have a value of 0081 less than 750. The best is less than 740 and the most preferred is less than IX z 1 ?

“oo - and in embodiment; The polymers of this invention have a melt index (MI) or (I) as measured by ASTM D-1238-E in the range from 1000 dg/min to 0 dg/min and better than UPR about 100 dg/min to about 100 dg/min; Better yet from about 10 dg/min to about ov 0 dg/min and most preferably from about 110 dg/min to about 01 dg/min. The polymers of the invention in one of the preferred embodiments have a flux index ratio (L121) Cua measured as:1 according to the ASTM-D-1238-F method ranging from 0 to less than Yo and preferably from about 11 to less than 1 Yo. The polymers of the invention in one of the preferred embodiments have a flux index ratio of (:D1/O1) (measured as , and O according to the ASTM-D-1238F method in excess of Yo and preferably in excess of Ye and preferably in excess of 00; preferably in excess of 00 and most preferably in excess of 66. In another embodiment as well; propylene-based polymers are produced In the process of this 1 - the invention. These polymers include asymmetric polypropylene, homoordered polypropylene and alternating polypropylene. Other propylene polymers include impact, retard or random copolymers of propylene. The polymers produced by the process of the invention are useful in forming processes such as © - forming a film, sheet or fiber by extrusion, co-extrusion, blow molding, injection molding, and rotary molding. Blow molded, co-extruded or laminated are useful as shrink films, suspension films, stretch films, sealing films, oriented films, snack wrappers, sturdy bags, grocery bags, vo wraps for baked and frozen foods, pharmaceutical wrappers, industrial liners and films. ..etc. for touching and non-contact uses 1 11

Cov - contact with food. The fiber industry includes spinning magma, swirling the solution, and blowing the magma to be used in woven or non-woven form to make filters or tissues for baby diapers, medical gowns, geotextiles, etc. Extruded materials include medical tubes, wire coatings, cables, geomembranes and pond liners. Molded materials include single- and multi-layer structures in the form of bottles, tanks or materials. Items include wide bowls, hard food containers, toys, etc. rad The following examples were provided for a more complete understanding of this invention, including its representative advantages, and the polymer properties were determined by the following test methods: The density was measured according to the ASTM-D-1238 method 0 and the dirt coefficient was shown. The Fouling Index in the tables below shows catalyst workability. Where the higher the value, the greater the amount of observable dirt. A soiling coefficient of zero indicates substantially no soiling or no visible soiling. A soiling factor of 1 indicates light soiling; Wherein, a thin layer of polymer is deposited on the stirrer blades of a polymerization reactor 1 containing a two-litre isobutane slurry and/or no lamination on the reactor body. And indicates the coefficient of dirtiness? on more than light soiling; Where a semi-greased ALE layer of polymer is deposited on the stirrer blades and/or the reactor body wall has minimal lamination with a bandwidth of 1 to 1 inch (Y.08 to 5.068 cm) on the reactor wall. Jus the smudge parameter on a medium smear; Wherein a thicker latex-like polymeric layer is deposited on the stirrer blades and some of the reactor soft blocks and/or a little lamination on the reactor body with a bandwidth of ? to * inches (5.08 to VAY cm) on the reactor wall. and indicates the soiling coefficient; on more than average soiling; Wherein a thick latex-like polymeric layer and/or some solid polymeric lumps or spheres and/or laminations are deposited on the reactor body wall with a bandwidth of JY; inches (from 0.17 IVY cm).

- because - the efficiency shown in the tables below is measured by the number of grams of polyethylene (PE) ethylene per gram of polymerization catalyst per hour (21 g/g of catalyst. hour) comparison example (1) os catalyst (a)

° Use dimethylsilyl-bis(tetrahydroindenyl) zirconium dichloride (Me,Si(HaInd),ZrClz) dimethylsilyl-bis(tetrahydroindenyl)zirconium dichloride; Provided by Albemarle Corporation of Baton Rouge; Louisiana as the metallocene-type bridge catalyst containing a bulky ligand used in the comparison example Ja Cua (1). (Me,Si(HiInd),ZrCly) catalyst

ev dehydrated at Crosfield 128-70 ES-70 on 168 lite Crosfield silica 0 (LOI) Loss on Ignition by weight of water lost on ignition #1 DM contains approx. Determination of the lost weight of the heated carrier stored at LOI dad measured 158-70 Crosfield silica hour. Silica YY DM for about 0 has an average particle size of £0 µm and is available from Crosfield ES-70

0 Limited 40 Warrington, England.

The first step in making the large ligand-containing metallocene mobile catalyst described above involves the formation of a precursor. wherein 460 lb (Yd) of Jha toluene and desiccant are added to a stirred reactor and then 0101 lb (£AY) of 1980 by weight MAO methylaluminoxane is added in Y: toluene (available from Albemarle Corporation 6+ in Baton Rouge, Louisiana). Add 9497 lb (ET kg) of BY by weight from a solution of dimethylsilyl-bis(tetrahydroindenyl) zirconium dichloride and 1010 lb (YVY) kg) of toluene added to the reactor. Then the predecessor solution is stirred at a temperature ranging from 80 df

ve (degrees Fahrenheit) to 100 df (i.e. 77.7 dm to TVA dm) for one hour.

oA - - while stirring the above-prepared predecessor solution; 8500 lbs (YA) kg) of a support material of dehydrated silica at 100 dm of Crosfield type is added slowly to the precursor solution and the mixture is stirred for a period of 1 minute at a temperature ranging from From Ae BD to 001 DF (from 76.7 BD to 7.8 BD). After the completion of the Aida Vo, 0 74060 lbs 01 (kg) of toluene solution of concentration 701 by weight is added containing SSN (N) (7-hydroxyethyl) octadecylamine (N,N-) bis(2- hydroxylethyl) ((C13H;37N(CH,CH,0H)) octadecylamine type 85-990 Available aul Kemamine AS-990 AS-990 from Witco Corporation of uae, Tennessee, with an additional 1,011 lbs (00 kg) of 0 toluene lye and then mix the contents of the reactor for 0 minutes, heating to 16 dF (pd VA) and then 01 min LL vacuum and dry the polymerization catalyst mixture at 17/8 dF (pro VA) for about 1 hour until a smooth flowing powder is obtained. The weight of the final polymerization catalyst was 1701 lbs (024 kg) and the dy all of Zr by weight was 70+ and the mol percentage by weight was AY (1) Jia 0. Catalyst preparation (b): Weighed A sample of 1 kg of polymerization catalyst prepared as described in comparative example (1), ie catalyst (a) and placed in a © liter glass flask under an inert atmosphere. AISt) Witco Aluminum Stearate #22 YY No. (YY i.e. 1-1 “(011:)011(::000) supplied by Witco Corporation of Memphis, Tennessee; vacuum drying at AG dm was added to the flask and the contents were stirred and mixed for 10 minutes at room temperature.It appeared that aluminum stearate was dispersed homogeneously through the catalyst particles.Example (1?)

Con - A sample of 1 kg of the polymerization catalyst prepared as described in comparison example (1), i.e. catalyst (1), was weighed and placed in a ? liter glass vial under an inert atmosphere. 0 Cid g of Sug Aluminum Stearate (AlSt) Witco Aluminum Stearate # 22 71 YY (CH3(CHy)16CO0)2 Al-OH supplied by © Witco Corporation in Memphis, FL and was added to the flask and the contents were stirred and mixed for 10 minutes at room temperature.It appeared that aluminum stearate was uniformly dispersed through the catalyst particles.Example (©”) Preparation of the catalyst (d) A sample of 1 kg of the polymerization catalyst prepared as described in the comparison example (oY) i.e. the catalyst (1) was weighed and placed in a ? liter glass flask under an inert atmosphere. 0 dh, g of Sug Witco Aluminum Stearate #22 YY (50l YY (CH3(CH,)16CO0), Al-OH supplied by Witco Corporation 0 of Memphis, Tennessee; Dim blood was dried in a vacuum and added to 1- the flask and the contents were stirred and mixed for 10 minutes at room temperature. The aluminum stearate appeared to be uniformly dispersed through the catalyst particles. Polymerization process using A to D catalysts fed a two-liter autoclave reactor in the presence of a nitrogen scrubber stream with CAT mmol of triethylaluminum and then with 10 cm of ve monomer The covalent 1-l-hexene and 6800 cm of dilute isobutane and the reactor contents were heated to A dm were then 100 mg of each of the mobile polymerization catalysts prepared above; i.e. catalysts (a), (b), (c) and (d); separately and using the following method: each polymerization catalyst was simultaneously added with ethylene to the reactor to obtain a total reactor pressure of YYO psi' (7740 kPa). Ye kept the reactor temperature at AO dC and allowed the polymerization to continue for 560 minutes. and after GBB) 0 z 11

qe - Cool the reactor, drain the ethylene, dry the polymer, and weigh to obtain the polymeric product. Table 1 below presents the resulting activity data as well as the fouling properties observed using catalyst 0, which is free of aluminum stearate, and catalysts (b) through (d), which contain different levels of aluminum stearate. ° Table 1 g: 91 / g catalyst hr 1 Te | stearate on the efficiency of the catalyst and its workability Comparison example (Y) Preparation of the catalyst (E) First fed 1 liter of toluene 0110 toluene g of 0 methylalumoxane solution of concentration 701 by weight in toluene (available from Albemarle Corporation, Baton Rouge, Louisiana) and then 7.1 g of 11-dichloride (Jpg ha-cyclopentadienyl) bis(1,3-methyln-butyl) zirconium cyclopentadienyl) zirconium dichloride as a solution of 01 concentration in toluene to a 1-gallon (7.2097 L) reactor. The mixture was stirred for 10 minutes at room temperature, after which AO g of silica was added. silica (type 544 Davison

- - 8 dehydrated at 0,010 DM and supplied by cu yan Jl slid Davison Chemical Division ¢W.R.

Grace, Davison Chemical Division, Baltimore; maryland) to the liquid while stirring slowly 0. de pu increased the stirring for about jie minutes to ensure the dispersion of silica 8 in JL and then an appropriate amount of toluene was added to form a liquid-to-solid slurry 0 It has a degree of cohesion of ; anf au and continued mixing for 10 minutes at 171 rpm after which 1 g of Kemamine 85-990 AS-990 (supplied by Witco Corporation of Memphis, Tennessee) was dissolved in 100 cm of toluene, then add the product and stir for 11 minutes. Then the drying was carried out in a vacuum and in the presence of a nitrogen-cleaned stream at 11/8 dF (9.4 dF). When the polymerization catalyst comprising 0 on a silica support seemed to flow smoothly; It was cooled to a lower temperature and emptied into a nitrogen-cleaned vessel and approximately 1 kg of polymerization catalyst was obtained dry due to some loss due to drying. z Example (;) “on catalyst (f) vo A sample of the polymerization catalyst prepared as described in comparative example (7), i.e. catalyst (e), was a synthesis in dry form with an amount equal to LY by weight of Witco Aluminum Stearate # 22 YY (AIST) (supplied by Witco Corporation of Memphis, TN) based on ASH weight of the portable polymerization catalyst. AlSt No. YY in a vacuum oven for VY an hour at 88 dm, then Wolff© catalyzed the polymerization by dry synthesis in the presence of nitrogen using AlSt No. YY. Table (Y) shows the benefits of adding carboxylate carboxylate salt metal salt in this process i.e. aluminum stearate to the polymerization catalyst These examples also show that the carboxylate metal salt has almost no effect on the properties of the molecular weight of the formed polymer.

The results of the polymerization experiments for catalysts (e) and (f) using the same process as previously described above for catalysts (a) to (d) are shown in the table below. Schedule Y 7 by weight 21g/g catalyst. hour) | dirt | decigrams/minute | Magma (Ll) Y for Tw Tel we Ta 0 Comparison example (Fr) A Catalyst (g): Feed 0101 gm of activated solution of methylalumoxane (MAO) methylalumoxane Its concentration is 7/70 by weight in toluene (PMAO) toluene, which is a modified MAO available from Akzo Nobel Laporte; Texas); Then 0.© liter of toluene is added to a ¥ gallon (7.097 L) reactor ys. During the cui add 1.” g of Jigme Jha VY bis(1,3-methyl-n-cbutylcyclopentadienyl) zirconium dichloride which is a g catalytic compound 5 Oe metallocene containing bulk ligand as a solution of concentration TA by weight in toluene to the reactor and the mixture was stirred for Te min at room temperature to form -1 catalyst solution.The contents of the reactor were emptied into a flask AC g dehydrated silica at Tee dm (available from Crosfield Limited, Warrington, England) was fed to the reactor.The catalyst solution in the flask was then slowly added to a carrier of silica in the reactor while stirring slowly. An additional amount equal to YOu cm of toluene was added to ensure obtaining the required degree of hardening and the mixture was stirred ve for an additional 01 min. 1 g of chemamine was added Type AS-990 Kemamine AS-990 (available from Witco Corporation 1171160 Memphis;

Cay, Tennessee) as a solution of 701 in toluene 1010606 and stirred for 30 minutes at room temperature. Then the temperature was raised to TA dem (100 dF) and a vacuum was applied to dry the polymerization catalyst. Drying was continued for about +7 hours with slow stirring until the polymerization catalyst appeared to flow smoothly. It was then emptied into a flask and stored in 0 nitrogen atmosphere, obtaining 10011 g due to some loss in the drying process. The analysis of the polymerization catalyst showed that the percentage of zirconium - 70.7 by weight and the percentage of aluminum = 1018 aluminum by weight Examples (0) and (1) in Examples (0) and (1) Injection of the polymerization catalyst prepared according to what was described in the comparison example (© catalyst (g); with 74 by weight and 78 by weight of YY Witco Aluminum Stearate #22 1.151 (YY) (available from Witco Corporation, Memphis, Tennessee) based on the charge of the catalyst and injected into the polymerization reactor.The results of the polymerization experiments using catalysts (g), (h) and (i) in the same process as previously described for catalysts (a) to (d) are shown in table (©) below. Y vo / wt g aa/PE catalyst dh hour deg/min magma L/L; soiling 1 dl flan" aa we The table (©) shows that with the use of more catalyst An event of 2S soiling exposure that aluminum stearate is effective It also shows that aluminum stearate does not substantially change the properties of the product AES) from () to (11)

- $4 - Examples (V) and (A) use the same catalyst described in the comparison example oF) i.e. catalyst (g) with (CaSt) calcium stearate (catalyst (cs) as the carboxylate metal salt in Example (V) and zinc stearate (ZnSt) (catalyst K) in Example (A) CaSt and 7205 are both available from Mallinckrodt Corporation <Mallinkrodt Corporation, Philippine, N.J. The polymerization process used to test the two catalyst compositions according to Examples (V) and (A) was identical as described and used above for catalysts (A) through (D). Examples (1) and (1) are used VY) the same catalyst as described in comparison example (1); i.e. catalyst A with aluminum stearate 0000166 aluminum (Example 4) (catalyst 0 (l)) being used as a carboxylate metal salt 01-5166 aluminum stearate (Example (10); catalyst (M)) and aluminum tri-stearate (Example (11); catalyst (N)) The polymerization process is described later in this Statement It will be used in examples from (VY) to (11); to test the catalyst compositions according to examples (3) to (11), i.e. catalysts (l), (m) and (n). The table (£) below presents these results. Table; 1 | m | Cae | ems | 0 lage

Cr Tes + [ele

Aluminium. Examples (7) and (A) show the use of different carboxylate metal carboxylate salts. Specifically, in Examples (7) and o(A), stearate metal Ca 70 and Ca 70 are shown to be effective in reducing fouling. Examples (9), (01) and (11) show many types of carboxylate aluminum salts, especially those different active forms of aluminum | 0. It is noted from the data in Table (4) that the first compounds Second and third stearate are the most effective Examples (VY) (10) In examples (VY) through (V0) use the dry synthesis method described in Example (1) with catalyst (a ) for comparison example (1); with different types of metal carboxylate salts

carboxylate metal salts 01 Table (©) shows the quantity and type of carboxylate metal salt. The following polymerization process described below was used for each combination of the polymerization catalyst and the carboxylate metal salt, i.e. catalysts (S), (P) and 05 Polymerization process for catalysts from (1”) to (10)

“oss Yo then (TEAL) triethylaluminum aluminum Ji mmol of tri-VT fed Vo of the comonomer 1-hexene 1-1606 and 8060 cm” from a dilute isobutane to an autoclaved reactor capacity of two liters in the presence of a clean stream of nitrogen, isobutane mg of each mixture of 100 DM then polymerized and reactor contents were heated to .. 8 described above; carboxylate metal salt portable polymerization catalysts and metal carboxylate salt ,

Saal) | 0 00 (with specified amounts of carboxylate metal salt as listed in Table (5)); Separately Bay for the following method: each combination of polymerization catalyst and carboxylate metal salt was added simultaneously with ethylene to the reactor

-10+- for a JS reactor pressure of 78 psi" (740 ?kPa) and the reactor temperature was maintained at 88 dC and the polymerization was allowed to continue for 500 min. After 0 min; The reactor was cooled, the ethylene was drained, the polymer was dried and weighed to obtain a polymeric product. And (V0) it turns out that it is preferable to have a large group of R on carboxylate metal Hall salts, specifically aluminum carboxylate metal salts Table © 1 9 | Sun | des a dad | | a: 6 | aq | dew ha except a b | lat lum | e Plaiting Examples from (11) to (VA) and comparison example (4): Examples (076) and (VY) and (VA) and comparison example (£) that the effectiveness of using a metal carboxylate salt +88 L carboxylate metal, especially aluminum stearate, in a gas-phase process using a fluidized bed (a) fio with a catalyst system of Metallocene eo has a large day to produce polymer classes that are normally difficult to produce and especially Lad is related to workability. It is usually difficult to produce varieties with a higher fractional magma index and density if one considers the operability of the reactor. The polymerization catalyst used in the polymerization processes according to ABN (11), (VY) and (1A) was worked in a process to be described below and the results are shown in Table (1) below. vy. Polymerization process cv -

Catalysts (1), (b) and (5) described above were tested separately in a gaseous reactor

Continuous fluidized bed phase contains 1 nominal reactor, Bale, VA inch in length and diameter

Internal measures 16.5 inches. The fluidized bed consists of polymeric granules. Streams are mixed

Gaseous feeding of ethylene, hydrogen and liquid co-monomer lee

0 in a T-mixing system and added below the reactor bed to the recycled gas line. And use

1-hexene-1 as the comonomer. Individual flow rates were controlled for each

Ethylene, hydrogen, and the co-monomer to maintain properties

the desired specific structure. Adjust the concentration of ethylene to maintain a constant partial pressure

of ethylene and adjust the hydrogen concentration to maintain a constant molar ratio

0 > for hydrogen to ethylene and measure the concentration of all gases by means of

Continuous gas chromatography to ensure relatively stable composition in the recycled gaseous stream. and injected

Portable solid metallocene catalyst system containing ligand

huge shown in Table (6); directly to the fluidized bed using nitrogen

Purified at 1.0 lb/hr (TA) .+ kg/hr. The interacting layer was preserved for particles

1 The polymer developing in Alla fluidized by continuous flow of supplementary feed and recycled gas

Rotation through the interaction layer. An apparent gas velocity of 1 to + was used

Spd (705 cm/s to 90.4 cm/s) to achieve this. The reactor was operated under total pressure

of 7051 lb/in” (7059 kPa) and a reactor temperature of AO dm

And an apparent gas velocity of 7.76 ft/s to achieve the required liquefaction of the particles. And to keep

© At a constant reactor temperature, the temperature of the recycled gas was set in the Jal gia form

To accommodate any changes in the rate of heat generation due to polymerization. The fluidized bed was kept at

Fixed height by drawing part of the layer at a rate equal to the formation rate of the particulate product.

Semi-continuous transfer of product by means of a series of valves to a fixed chamber

volume; which is drained back into the reactor at the same time. This allows the product to be removed uniformly

ve is highly efficient and at the same time recycles a large part of the unreacted gases into

TA - - reactor. This product is cleaned to remove evaporated hydrocarbons and treated with a small stream of moistened nitrogen Jil to remove any trace amounts of the remaining catalyst.

a - table 3 se a — on re ee ewe | Uma | a | on | a | ar | any | (1) ems refers to the unit pound of polymer per pound of polymerization catalyst, and by using carboxylate metal salts yall in combination with 0 polymerization catalysts, the operability of the reactor is greatly improved. Table (1) shows A gas-phase reactor operated without any problems in the production of polymers with a fractional magma index for several class transitions (Lass 870). It is specifically shown; it is using a polymerization catalyst without a carboxylate metal salt (carboxylate metal salt) as described in the comparison example (4). (without aluminum stearate) the reactor stopped due to sintering and lamination in less than “0 stratification shifts at a flux index of about dg/min and a density of AVAA + g/cm”. In an embodiment of the invention, the process is run for a period Time of more than; stratification shifts, and it is better to be more than © stratification shifts, and most preferably more than “stratification shifts. And to obtain a Laie stratification transformation, the total weight of the polymer discharged from the reactor is exactly equal or almost equal to the weight of the layer in the reactor. Vo has It is known in the technique that reducing the bulk density of the resin may improve the workability of a polymerization process, specifically a gas-phase fluidized-bed polymerization process. It is noted from Table (1) that the bulk density of the resin did not change much, but the workability of the process according to the invention was amazing.

and substantially improved when the carboxylate metal salt was combined with the polymerization catalyst. Maths ¢ (V4) Preparation of a conventional type transition metal catalyst and preparation of a conventional type transition metal catalyst from a mixture generally containing a magnesium compound 0188085101770 for example 148012 and a titanium compound for example and 10 1101:.1/3 an electron donor eg tetrahydrofuran (1117); And loaded on dehydrated silica at 001 dm. A detailed description of the preparation procedure can be found in the US Patent 4 OFA (EY) which is incorporated in 0 herein for reference. The specified catalyst composition had a molar ratio of TNHAL to THF of 79 and a molar ratio of DEAC to THE of 773 where TNHAL is DEAC tri-n-hexyl aluminum methylated chloride diethyl aluminum chloride .aly 3 process using 318 (ha, RIT) catalyst conventional type vo injection of the dry-flow smooth catalyst described above; into a continuous fluidized bed gas-phase reactor comprising 00 A nominal accessory reactor of length VA in (0.V cm) has an inner diameter of 176.6 inches (1.93 lb cm); As described earlier in this description. However, in this process 8 by weight of TEAL triethylaluminum, a conventional co-catalyst in hexane solution, was continuously added to the reactor to maintain a certain concentration of TEAL in the fluid bed of Vr cfa m (ppm). The transition metal catalyst of the conventional solid type prepared according to what was described in the previous paragraph was also injected directly into the fluidized bed, see Table (7); Experience (). A solution of 00018 gfm (ppm) was prepared from carboxylate metal salt veo, which is Witco Aluminum Stearate No. Witco YY

Y \ - - AlSt) Aluminum Stearate # 22 No. (YY) in hexane and during the polymerization process, as shown in Table (7); Experiment (a) 0 Pumping the solution into a phase gas reactor Results see table oY) Experiment (b). Where it is noted that the catalyst yield achieved by J gall equilibrium is almost the same even after the addition of 1 aluminum stearate 0. In addition to that; The operability of the reactor in this example remained constant and continued for more than; Layer transformations before optional termination of the experiment. Table (V) God of God ae | sansa | aaa og mais | l vr average particle size (1) denotes the number of grams of polymer per gram of catalyst 1 The above example shows that the use of carboxylate li metal salt coupled with a transition metal catalyst system of a conventional type that does not spoil the workability in a continuous polymerization process in a gas phase, especially when the carboxylate metal salt is added separately from the catalyst system of the traditional type 0, however, it was found in some experiments The polymerization processes in the sludge phase that run in batches showed that the use of Witco Aluminum Stearate 00 class E A in a dry form combined with a conventional titanium-containing metal catalyst led to a decrease in productivity. without being bound by any particular theory; It is believed that the reduction in productivity may be due in part to the reaction of aluminum stearate with the catalyst.

The co-catalyst of the conventional type, for example driethylaluminum, which leads to a decrease in the effectiveness of the co-catalyst in the batch reactor. Examples (01) and (11) below illustrate the use of a conventional metal catalyst containing chromium in a dry form combined with a carboxylate metal salt. Example (01) A catalyst is prepared with 18 J of A conventional type containing chromium prepared a metal catalyst of a conventional type containing chromium known AIS as a Phillips catalyst using a Crosfield EP510 EPS10 catalyst (containing #1 By weight titanium and 0.9 by weight chromium from chromium acetylacetonate supplied by Crosfield Limited Warrington, England. The catalytic activity of type 20510 at 800 dm using a mixture of oxygen 555 2 790 and nitrogen of concentration 771 in a fluidized bed column as known in the technique and used in the following polymerization process. 0 μmol of triethylaluminum (TEAL 775 by weight in heptane) to a 7.7 L autoclaved reactor as a scavenger to remove trace impurities in the vessel. 8060 mL of isobutane polymerase grade available from Phillips Petroleum Bartlesville © Oklahoma was added to the reactor. The contents were stirred at a speed of 1,000 revolutions per minute, and the temperature of the reactor was raised from ambient temperature to 97 d.m. Then ethylene was added to the reactor until the total pressure reached 75 psi (kPa) and then Yoo was fed mg of activated chromium catalyst prepared above in example (01) to the reactor and the polymerization of ethylene continued for about 10 minutes deg this stage xe finish the reaction by draining the hydrocarbon compounds from The reactor

This comparison example is (0?a); The chromium catalyst prepared in the manner described above was used in a pure form (without aluminum stearate), and this led to the production of an electrostatically charged polymer, Je, and a hexane solution of the antielectrostatic agent Kemamine AS-990 AS- 990 Removing the electrostatic polymer from the walls of the reactor. The total weight of the resin was about Vio g. Example (+) In this JB the polymerization catalyst contained 00 mg of activated chromium catalyst (prepared According to what was described above in Example (01) dry blended with 10 mg of aluminum stearate and Witco Aluminum Stearate 0 class BA before polymerization, then the polymerization catalyst was fed to the reactor at the same time. Polymerization conditions described above in comparison example (17a). After about 610 minutes, stop the polymerization reaction and float the reactor. The resulting resin was not electrostatic and the polymer was removed from the reactor easily. The weight of the resulting resin was 17 g0 This experiment showed that The carboxylate metal salt all of aluminum stearate may prevent the formation of charges on the resin made or equivalent to use for a conventional type metal catalyst system containing chromium. There is a general belief that the phenomenon of plating the reactor In the gas-phase polymerization of ethylene using a chromium catalyst it is related to the static charge in the system. Example (YY) | Copolymerization Process 0 μmol of triethylaluminum was added to the reactor with its scavenger adsorbent removing trace impurities present in the vessel. Then 50 mL of purified comonomer of 1-hexene-l and 8060 mL of isobutane were added to the reactor. and after raising the temperature to 85 dm while stirring at a speed of 1,000 revolutions per minute; ve ethylene was added to the vessel until the pressure was 75 “lbs/in” (YOAT) kPa). then

vg - 701 mg of polymerization catalyst was fed to the reactor and the polymerization process continued for a certain period of time. Then finish the reaction by draining the hydrocarbons from the reactor. All of the following examples were performed using this polymerization process. However, in some examples the amount of 1-hexene-1 was different and the reaction times were different.

(YY) Comparative example 0 Any polymerization catalyst to the reactor “ait chromium mg of chromium catalyst 00000 feed min. And in 01 for about (YY) and the polymerization process continued in the manner described above in the example in a pure form, that is, without chromium stearate. This catalyst was used as chromium (YY) in the comparison example, which led to the contamination of the reactor. Heavy polymeric layers of aluminum stearate were observed on the reactor walls, stirrer and internal thermocouple. And agglomerates most of the amount of the polymer

down the reactor. The total amount of viscous resin was of g. Example (?=) In this example, Foo mixed 1 mg of the activated chromium catalyst prepared above in Example (71) in dry form with 10 mg of aluminum stearate, which is 0 is WETCO Witco Aluminum Stearate, class EA, and the polymerization process was used in the manner described above in the example (11). After 40 minutes, the experiment was stopped by discharging the hydrocarbon compounds, and it was found that the contamination of the reactor was much lighter than in the comparison example. (17a). Only a light polymeric layer was observed on the stirrer, thermocouple and reactor wall. The total amount of resin formed was about 110 g. © > Comparison example YV) = (Comparison example YY) c) This is done by following Same polymerization process as described in example (YY) except using Yo mL of 1-hexene 16606-1. 018 mg of activated chromium catalyst was used as described by Del in (Y)) Jad, pure, that is, without any aluminum stearate. The polymerization reaction continued for 50 minutes, then the contents were drained from the ve. The reactor and Owen. Severe soiling was observed in the reactor. A polymeric ring of about ?

vo - inch (.67 cm) on the top surface of the reactor with a thickness ranging from YO 0a to 1785 in (174 to 0191 cm). A polymer sheet formed on the bottom of the reactor wall. The total amount of resin produced was about VTA gram. The polymer formed was so bulky that it was difficult to determine the density of the polymer. 0 Example (av)z This Example (1?d) was conducted following the same polymerization process as described in Example (YV) except using 1mL Yo-hexene-l-hexene and mixing 100 mg of the same activated chromium catalyst used in the comparison example (17c) in dry form with 10 mg of aluminum stearate Witco Aluminum 0 51681816 class EA and the polymerization reaction continued for 00 minutes, then the contents were drained from the reactor and filtered. A very thin polymeric layer was found on the stirrer and the thermocouple. and the reactor wall. The amount of the resulting polymer was 14 g and its density was 0.9747 g. Name This invention is directed in one of its embodiments to a continuous process for the polymerization of two ethylene and at least one alpha-olefin containing of? to 0 carbon atom in Ve, the presence of a polymerization catalyst comprising a metal catalyst of a conventional type containing chromium and a zy carboxylate metal salt a polymeric product having a density of less than AE g/ cm" to about 051 g / cm "and it is preferable that it be less than 1.34 fas, and it is better that it be less than Canvas 197, and it is better that it be less than Canvas AYA, and it is preferable that it be less than 197 g / cm." In a preferred embodiment the continuous process is a #0 gas-phase process operated at pressures from 0,001 psi (kPa) to about rr psi (7759 kPa) and at a temperature of more than From 0 dm and preferably from 1 dm to 111 dm. It is also preferable to operate the process in a condensing manner, where liquid and gas are added to a fluidized bed reactor containing a dilute medium and where the condensate gas level is higher than TA by weight and preferably higher than 1010 and most preferably higher than 17 to the limit of ve 00 based on the total weight of the fluidizing medium entering the reactor.

Va for the Intensive Method process. Consider American Patents Nos. 5,247,744 and which are fully incorporated into this release for reference. 0.1.4 Although the present invention is described and illustrated by reference to certain embodiments; However, those savvy in the technique will be aware that the invention may include changes that may not necessarily be described in this statement. for example. It should be understood that salt 0 may be added to the reactor in addition to being in contact with the carboxylate metal salt catalytic system according to the invention. It is also recognized that the process according to the invention can be used in a polymerization process in a metallocene cascade reactor. for example; A portable metallocene type catalyst system is used in a carboxylate metal salt reactor containing a bulky ligand free of a metal carboxylate salt containing one metallocene ligand and a portable metallocene type 0 bridge catalyst system is used in another reactor or A bulky carboxylate metal salt that may come into contact with a carboxylate metal salt, i.e., “carboxylate metal salt,” vice versa. It is also understood that the components of the metal carboxylate salt, for example, the hydroxy compound Hl and the compound carboxylic acid, the metal carboxylic acid, may be added to the reactor or to the polymerization catalyst to form them in the reaction site, or with hydroxy, the carboxylate metal salt may be il the catalyst. It is also recognized that the 0 carboxylate salt is carried separately on a carrier different from the polymerization catalyst and a portable polymerization catalyst is preferred. For this reason only the appended claims should be referred to for the purpose of determining the actual scope of this invention.

Claims (1)

_- unless - Claims 1-1 A catalyst composition comprising a combination of a polymerization catalyst comprising a metallocene catalyst complex 7 containing an Atay bulky ligand and a metal carboxylate salt ¥ of group ¥ or of group 11 where <i is not for the polymerization catalyst and the metal carboxylate salt is a reaction product. 1 ?- The composition of the catalyst according to claim 1, where Jha is the metal carboxylate salt Y of the formula: MQL(OOCR), v ; Where M is a metal of the group ? Or 1” of the periodic table of elements Q represents ° halogen or hydroxy group <hydroxy alkyl alkoxy 1 aryloxy 7 siloxy ssilane silane or sulfons R ¢sulfonate Jia 7 radical hydrocarbyl radical Ju Ss ue contains who? to 001 carbon atoms x ¢carbon A is an integer from zero to ?; y represents an integer ranging from 1 to ;; The sum of # and the valence of metal M is equal to 0 *- catalyst composition according to claim ¥ where 1 represents Wy or 14 represents a metal of 7 group 1 or : 0 represents a hydroxy group and Ja R crack 7 hydrocarbyl contains more than 11 carbon atoms 1 carbon ;- catalyst composition according to claim 1 where the carboxylate metal salt Y has a melting point ranging from 001 mm (Asie class) to 0.00 m. - Y-- -o 1 catalyst composition a, of claim 1 where the carboxylate metal salt Y is a stearate compound. carboxylate where the metal carboxylate salt 1 of protectant a, catalyst composition 1-1 is selected from a group consisting of metal salt Y aluminum di-stearate caluminum mono- stearate ¥ and combinations thereof. aluminum tri-stearate 0 7- Composition of the catalyst, By, of claim 1, where the polymerization catalyst is a portable polymerization catalyst, Y, containing a carrier 1 + “- catalyst composition according to claim 1 where the polymerization catalyst also includes a Y carrier and a catalyst and where the catalyst complex contains metallocene v which contains a bulky ligand On an atom of titanium ¢ zirconium or hafnium metallocene, where the catalyst compound metalocene 1 represents the catalyst structure according to claim 4-1 with the formula: bulky ligand containing a bulky ligand Y (CsHa.aR)Ax(CsHaaR)MQg-2 ¢ ° where M is a transition metal chosen from group 4; © or 61 5 Jia (CsHaaRa) 1 large ligand derived from cyclopentadienyl bearing or without 7 substituents bonded to (M) each R represents a 33s hydrogen chydrogen substituent group containing A Contains no more than 0 atoms other than hydrogen atoms Hydrocarbyl 9 contains substituents or is devoid of them Contains from 1 to 71 carbon atoms “carbon” or 1 carbon atoms are bonded or more together to form part of a loop or system - for 1 ring with or without substituents and containing from 4 to 70 carbon atoms A carbon \Y represents a moiety containing a carbon atom 0 ; germanium silicon tin of phosphorous tin or nitrogen or its terminator combination and bridges two rings 1 of (CsHaaRe); And each © separately contains a hydrocarbyl hydride 31 to 1 cyclic or branched with or without substituents and contains clinear hydrocarbyl \o 5 a carbon atom ccarbon halogen alkoxide aryloxide “univalent anionic aryloxide or monovalent anionic ligand phosphide phosphide camide amide VY Cus dligand YA may form a moiety © of an alkylidene ligand or hydrocarbyl 1 cyclometal or anionic chelate ligand divalent anionic chelating ligand Ye other p represents an integer equal to the state of 1 formal oxidation of 04 d represents an integer chosen from zero (JT OX); .1 an integer equal to zero or x representing the degree of substitution; TY-01-1 represents the composition of the catalyst according to claim 1 where the weight percentage of H | Based on the total weight of the polymerization catalyst, metal carboxylate salt Y by weight. z 001 from 1009 by weight to v where the method includes the following two steps: lia method 0 to make a composition 1-11: (1) formation of a polymerization catalyst comprising a metallocene catalyst compound v containing a ligand sbulky ligand and ¢ (b) addition of at least one metal carboxylate salt choose > from group XY -1" 1 method Lay of claim 11 wherein the polymerization catalyst is dry and free-flowing Y and the carboxylate metal salt is in solid form. pain VY The method according to claim 11 where Ba is the carboxylate salt of the metal carboxylate metal salt Y of the formula: MQ, (OOCR), r : where 14 represents a metal from the group ? or VF from the periodic table of the elements; Every 0 represents ° separately a halogen or a hydroxy alkyl group 1 alkoxy, caryloxy, siloxy, silane, or 7 sulfonate ¢ each R separately reduces the hydrocarbyl radical A contains of? To New carbon atom x tcarbon represents an integer ranging from A zero to ; y is an integer hae ranging from 1 to ;; The sum of yx is 01 equal to the valence of the metal, tM. © represents a doped halogen; Or a 1-hydroxy Ry hydroxy group that represents a hydrocarbyl moiety containing of ; to 74 VY carbon atoms .carbon -14 01 The Gay method of claim 11 where the carboxylate metal salt Y has a melting point ranging from 100 C to 001 N . Gl where is the 11 carboxylate salt of claim Ga, method -1#© 01 stearate is a carboxylate metal salt Y 11-1 The method according to Claim 11 where the metal carboxylate salt Y is chosen from a group consisting of aluminum mono-stearate 1 aluminum di-stearate ¢ aluminum stearate aluminum tri-stearate and combinations thereof. -17 1 Method according to claim 11 wherein the polymerization catalyst is a portable Y polymerization catalyst containing a carrier harm -A- | 1 “oe by weight. 1 4- A method for making a catalytic composition; Where the method includes the analogous step: 4 0 Fusion of a polymerization catalyst comprising a metallocene catalyst compound containing 3 bulky ligands with a metal carboxylate salt 1 from group ? or . -71 0 The method according to claim 09, where the embedding period ranges from one minute to seventeen hours.