Gas phase polymerization process

Catalyst composition, methods of preparation and use in the polymerization process

Full description

Background of the invention:

This invention relates to a catalyst composition and methods for preparing the catalyst composition and using it in the olefins polymerization process. In particular, this invention relates to a method for preparing a catalytic composition from a metallocene-type system containing a bulk ligand and/or a conventional-type transition metal catalytic system and a metal carboxylate salt.

Advanced research in polymerization and catalysis has made it possible to produce numerous new polymers with improved physical and chemical properties for use in a wide variety of distinct products and applications. With the development of new catalysts, the choice of type of polymerization process (in solution, slurry, high pressure or gas phase) to produce a given polymer has expanded significantly. Also, advanced research in polymerization techniques has led to the creation of highly productive, economically enhanced and more efficient processes. Examples of this advanced research include, in particular, the development of the technology of using metallocene-type catalytic systems containing a bulky ligand. Aside from these cutting-edge technical researches in the polyolefin industry, there are still new common problems and intractables associated with process operability. For example, the ability of a gas-phase or slurry-phase process to form dirt and/or plaque is a difficult problem.

For example, fouling on the reactor walls in a continuous slurry phase process, which crosses a surface prepared for heat transfer, may cause numerous operability problems. Poor heat transfer during polymerization may lead to sticking of polymer particles on the reactor walls. These polymeric particles may continue to polymerize on the walls and may lead to premature shutdown of the reactor. Also, a small amount of the polymer may dissolve in the diluent

reactor and is deposited back onto the surfaces of the heat exchanger, for example metal, depending on the reactor conditions.

In a typical gas-phase continuous process, a recirculation system is used for several reasons, including the removal of heat generated in the process by polymerization. Expansion, plating, and/or static generation in a continuous gas-phase process may cause various reactor systems to not operate efficiently. For example, the cooling mechanism in the recirculation system, the temperature probes used to control the process, and the distribution board, if affected, could lead to premature failure of the reactor.

Several patents in the technology have addressed problems of operability in various processes and offered solutions to them. For example, US Patent Nos. 4,792,592, 4,803,251, 4,855,370, and 5,391,657 all describe techniques for reducing static generation in a polymerization process by adding water, alcohols, and/or Ketones and/or inorganic chemical additions for example to the process. The International Patent Bulletin pursuant to PCT No. 97/14721 issued on April 2, 1977 describes the suppression of particles that may cause lamination by adding an inert hydrocarbon to the reactor; US Patent 5,627,243 describes a new type of distribution plate for use in gas-phase reactors containing a fluidized bed. US Patent Publication No. 96/08520 describes exhausting the addition of a scavenger to the reactor. US Patent 5,461,123 describes Using sound waves to reduce delamination describes the US patent 5.66.736 and European Patent 0546252 A1 Adding an activity inhibitor to the reactor to reduce agglomerations. US Patent 5,610,244 relates to feeding a complementary monomer directly to the overbed reactor to avoid fouling and improve polymer quality. US Patent 5,126,414 describes the use of an oligomer removal system to reduce distribution plate fouling and the production of gel-free polymers. European Patent 453116 0 A1 issued describes the use of an oligomer removal system to reduce distribution plate fouling. On October 23, 1991, anti-electrostatic agents were added to the reactor to reduce the amount of plates and lumps. US Patent 4,012,574 describes the addition of a compound

A surfactant, for example a perfluorocarbon moiety, is added to the reactor to reduce fouling. US Patent 5,026,795 describes the addition of an antistatic agent with a liquid carrier to the polymerization zone of the reactor. US Patent 5,410,002 describes the use of a conventional Ziegler-Nata-type catalytic system carried on it. Titanium or magnesium, where a selection of anti-electrostatic agents are added directly to the reactor to reduce fouling. US patents 5,034,480 and 5,034,481 describe a reaction product resulting from the use of a conventional Ziegler-Nata titanium catalyst with An antielectrostatic agent for the production of ethylene polymers with very high molecular weight. US Patent 3,083,198 describes the addition of an amount of carboxylic acid depending on the amount of water in the ethylene polymerization process using organometallic catalysts containing titanium and aluminum in a liquid hydrocarbon medium. US Patent 3,919,185 describes the redig process. It uses a nonpolar hydrocarbon buffer using a conventional Ziegler-Natta or Phillips type catalyst and a multivalent metal salt of an organic acid with a molecular weight of at least 300.

Various other known methods for improving workability include coating polymerization equipment, for example treating reactor walls with chromium compounds as described in U.S. Pats 4,532,311 and 4,876,320, and injecting various agents into the process. For example, International Patent Publication No. 97/46599 PCT December 11, 1997 Feeding a portable, soluble metallocin catalytic system to a material-poor zone in a polymerization reactor, injecting anti-algae and anti-electrostatic agents into the reactor, and controlling the rate Polymerization, specifically when the process is started and the reactor design is rearranged.

Other patents in technology to improve process operability have described modification of the catalytic system by preparing the catalytic system in several ways. For example, methods in the technology include mixing the components of the catalytic system in a specific order, manipulating the ratio of different components of the catalytic system, changing 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 have been described in. Bulletins. And it has

Particularly described in the technical section are the preparation procedures and methods for producing bulky ligand metallocene catalytic systems, specifically portable bulky ligand metallocene catalytic systems with low denaturation potential and better workability. Examples of such patents include International Patent Publication No. 96/11961 issued on April 26, 1996, which describes an antielectrostatic agent as a component in a portable catalytic system for reducing fouling and delamination in a polymerization process in a gaseous, slurry, or liquid medium, and US Patent 5,283,278, which relates to polymerization The primer for a metallocene catalyst or a conventional Ziegler-Natta type catalyst in the presence of an antielectrostatic agent, and US patents 5,332,706 and 5,473,028, which used a specific technique to form a catalyst by impregnation. The first and US patents 5,427,991 and 5,643,847, which describe the chemical bonding of non-coordinated anionic activators and carrier materials, US Patent 5,492,975, which describes metallocene-type catalytic systems bound to a polymer, and US Patent 5,661,095, which describes the loading of a metallocene-type catalyst onto an olefin copolymer. and unsaturated silane and PCT International Patent Application Bulletin No. 97/06186 of February 20, 1997 describing the removal of organic and inorganic impurities after the formation of the metallocene catalyst of the same type and International Patent Application Bulletin No. 97/15602 of February 1 May 1997 describing readily portable metal complexes and PCT International Patent Application Publication No. 97/27224 of 31 July 1997 relating to the formation of a portable transition metal complex in the presence of an unsaturated organic compound containing at least one terminal double bond and the European patent 638 A2-811 which describes the use of a metallocene catalyst and an activator cocatalyst in a polymerization process in the presence of a nitrogen-containing electrostatic agent.

Although all of these possible solutions may reduce the level of soiling or delamination somewhat, some of them are expensive and/or may not reduce soiling and delamination to a sufficient level to successfully operate a continuous process, especially a commercial or large-scale operation.

Thus, it is advantageous to devise a polymerization process with sustained operability and enhanced reactor operability while simultaneously producing new and improved polymers. It is also highly advantageous to devise a continuously operating polymerization process with a more constant catalytic yield, reduced denaturation or delamination capability, and increased operating life.

General description of the invention:

This invention provides a method for making a new and improved catalytic composition for use in a polymerization process. The method includes the steps of incorporating, contacting, synthesizing and/or mixing a catalytic system, preferably a portable catalytic system, with a metal carboxylate salt. In one embodiment, the catalytic system includes a transition metal catalyst compound of a conventional type. In a more preferred embodiment, the catalytic system includes a metallocene-type catalytic compound containing a bulky ligand. It is useful to combine a catalyst system with a metal carboxylate salt in any olefin polymerization process. Preferred polymerization processes include gas phase or slurry phase processes, and the most preferred is the gas phase process.

In an embodiment, the invention provides a method for making a catalytic composition useful for the polymerization of one or more fibrins wherein the method includes combining, contacting, synthesizing and/or blending a polymerization catalyst with at least one metal carboxylate salt. In one embodiment, the polymerization catalyst is a conventional type transition metal polymerization catalyst and the better a conventional type portable transition metal polymerization catalyst. In the most preferable embodiment, the polymerization catalyst is a metallocene-type catalyst containing a bulky ligand and the most preferable is a metallocene-type portable polymerization catalyst containing a bulky ligand.

In a preferred embodiment, the invention relates to a catalyst composition comprising a catalytic compound, preferably a transition metal catalyst compound of a conventional type and preferably a catalytic compound of a metallocene type containing a bulk ligand, an activator and/or co-catalyst, a carrier, and a metal carboxylate salt.

In the most preferable method of the invention, the metal carboxylate salt is synthesized, preferably dryly synthesized, and more preferably dryly synthesized by stirring or liquefying, provided that the portable catalytic system or polymerization catalyst includes a carrier. In this most preferred embodiment, it includes:

Polymerization catalyst A metallocene-type catalytic compound containing at least one bulky ligand, an activator and a carrier.

In yet another embodiment, the invention relates to a process for polymerizing one or more olefins in the presence of a catalytic composition comprising a polymerization catalyst and a metal carboxylate salt. The polymerization catalyst preferably includes a carrier and preferably one or more combinations of a conventional type and/or catalytic compound. Metallocene type containing a bulky ligand.

In a preferred method for making a catalytic composition according to the invention, the method includes the steps of combining a metallocene-type catalytic compound containing a bulk ligand, an activator and a carrier to form a portable metallocene-type catalytic compound containing a bulk ligand and contacting a portable metallocene-type catalytic compound containing a bulk ligand with a salt Carboxylate metal. In a most preferred embodiment, the mobile catalytic system is of a metallocene type containing a bulk ligand and a metal carboxylate salt in an essentially dry or dehydrated state.

In an embodiment, this invention provides a method for polymerizing one or more olefins in the presence of a polymerization catalyst that has incorporated, contacted, combined, or blended with at least one metal carboxylate salt.

Detailed description:

This invention relates to a method for making a catalytic composition and to the catalytic composition itself. This invention also relates to a polymerization process having improved operability and production capabilities using a catalytic composition. Surprisingly, it was discovered that the use of a metal carboxylate salt in combination with a catalytic system significantly improved the polymerization process. What is particularly surprising is that the catalytic system is carried on a carrier material, and even more so when the catalytic system includes a metallocene-type catalytic system that contains a bulky ligand, and even more so when metallocene-type catalytic systems that contain a bulky ligand are more effective and/ Or the co-monomer is incorporated into it to a high degree.

Although he does not wish to adhere to any theory, he believes that these catalysts are of the metallocene type and contain a bulky ligand that is more susceptible to delamination and/or fouling. It is believed that the catalysts are...

Very high efficiency may produce intense heat that gets trapped in the growing polymer particles. These extreme conditions are theoretically believed to lead to high levels of delamination and/or fouling. It is also believed that polymers resulting from metallocene-type catalysts contain a bulky ligand that forms very strong polymeric sheets. Thus, it is difficult to break up and remove any of these plaques that may form in the reactor.

Moreover, it was highly unexpected that high-density fractional melt index polymers could be produced using a combination of polymerization catalyst and metal carboxylate salt with improved workability. This discovery was particularly important because it is known in the polymer industry that these types of polymers are difficult to produce when considering the operability of the process.

The use of the polymerization catalysts described below in combination with a metal carboxylate salt significantly improves process operability, significantly reduces delamination and fouling, improves catalyst performance, improves the crystalline morphology of the polymer particles without any negative effects on the physical polymer properties, and enables the production of a wider range of polymers.

Catalytic 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 bridged bulky ligand are particularly preferred. The following is a non-specific description of various polymerization catalysts useful in this invention.

Conventional type transition metal catalysts

Conventional type transition metal catalysts include the conventional Ziegler-Natta type and the Phillips type chromium catalyst which are well known in the technology. Examples of conventional-type transition metal catalysts are described in U.S. Patent Nos. 4,115,693, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359, and 4,960,741, which They are all incorporated herein fully by reference. Conventional type transition metal catalyst compounds that may be used in this invention include transition metal compounds

From groups 3 to 8, preferably 4b to 6b of the periodic table of chemical elements.

These traditional type transition metal catalysts may be represented by the formula: MRx, where M represents a metal chosen from groups 3b to 8, preferably group 4b and preferably titanium; R represents a halogen atom or hydrocarbyloxy group and X represents the valence of the metal M. Examples of R include but are not limited to alkoxy, phenoxy, bromide, chloride, and fluoride. Examples of conventional type transition metal catalysts where M represents titanium include, but are not limited to, TiCl4, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)Cl3, Ti(OC4H9)3Cl, Ti(OC3H7)2Cl2, and Ti(OC2H5)2Br2. And TiCl3.l/3AlCl3 and Ti(OC12H25)Cl3.

Conventional transition metal catalyst compounds based on electron-donating complexes of magnesium and titanium suitable for use in this invention have been described, for example, in U.S. Pats 4,302,565 and 4,302,566, which are fully incorporated herein by reference . The 4-(ethyl acetate) derivative MgTiCl6 is particularly detailed. UK Patent Application 2,105,355, which is incorporated herein by reference, describes various conventional catalytic compounds containing vanadium. Examples of conventional catalyst compounds containing vanadium include, but are not limited to, trihalides, alkoxy halides, vanadyl alkoxides such as VOCl3 and (VOC2(OBu), where Bu represents butyl and 3(VO(OC2H5), vanadium tetrahalides, and alkoxyvanadium halides such as VCl4 and (VCl3(Obu). Vanadium chelates, vanadyl chelates, and chloroacetyl chelates, such as 3(VOOl2(AcAc) and V(AcAc), where (AcAc) represents chloroacetyl chelates. Preferred conventional vanadium catalyst compounds include VOCl3, VC14, and VOCl2-OR, where R represents a hydrocarbon radical, preferably an aliphatic or aromatic hydrocarbon radical containing 1 to 10 carbon atoms, such as ethyl, phenyl, isopropyl, butyl, propyl, p-butyl, and isobutyl.

And tert-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium chelate.

Examples of conventional chromium catalyst compounds, often referred to as “Phillips-type catalysts,” that are suitable for use in this invention are CrO3, chromosine, and silyl chromate.

chromyl chloride (CrO2Cl2), chromium 2-ethyl hexanoate, chromium chelate (3(Cr(AcAc)), and the like. Non-specific examples are described in US Patent Nos. 2,285,721, 3,242,099, and 3,230,550, which It is incorporated into this statement by reference.

Other conventional type transition metal catalyst compounds and catalytic systems suitable for use in this invention are described in US Patent Nos. 4,124,532, 4,302,565, 4,302,566, and 5,763,723, and European Patent Bulletins A2.0 416 815 and 436 420 0 Al, all of which are incorporated into this statement by reference. Transition metal catalysts of the conventional type according to the invention may also have the general formula M,tM2t”YuE, where 'M represents Mg and/or Mn and/or Ca and t represents a number ranging from 0.5 to 2 and ,,M represents a transition metal selected from Ti and /or V and/or Zr, and , where R represents the hydrocarbyl radical, in particular the alkyl and aryl radical, cyclic alkyl, aryl alkyl, or acyl chelate anion, in an amount that achieves The valence state of 'M, u represents a number ranging from 0.5 to 02, and E represents an electron donor compound chosen from the following classes of compounds: (a) esters of organic carboxylic acids; (b) alcohols; (c) effects; (d) amines; (d) Carbonic acid esters; (f) Nitriles; (g) Phosphoamides; (h) Esters of phosphoric acid and phosphoric acid; (i) Phosphorus oxychloride. Examples of compounds that apply the formula shown above include, but are not limited to:

And Mg3Ti2Cl12.7CH3COOC2H5 and Mg3Ti2Cl12.7CH3COOC2H5 and MgTiCl5.6C2H5OH and

MgTiCl5.100CH3OH and (tetrahydrofuran). MgTiCl5 and MgTi2Cl12.7C6H5CN and

Mg3Ti2Cl12.6C6H5COOC2H5, MgTiCl6.2CH3COOC2H5, MgTiCl6.6C5H5N,

N(C6H5)2.3CH3COOC2H5 and MgTiCl55(OCH3).2CH3COOC2H5MgTiCl5 and

MgTiBr2Cl4.2(C2H5)2O, MnTiCl5.4C2H5OH, Mg3V2Cl12.7CH3COOC2H5, (iv)

Hydrofuran)MgZrCl6.4. Other catalysts may include cationic catalysts such as ACl3 and other cobalt and iron catalysts that are well known in the technology.

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

Conventional type co-catalysts

The conventional type co-catalyst compounds may be represented by the conventional type transition metal catalyst compounds shown above with the formula M3M4VX2CR3b-c, where M3 represents a metal selected from groups 1a, 2a, 2b, and 3a of the periodic table of elements, M4 represents a metal from group 1a of the periodic table of elements, and V represents A number equals 0 or 1. Each Contribution Other conventional-type organometallic catalysts for the conventional-type transition metal catalysts given above have the formula M3R3K, where M3 supplies a metal chosen from groups 1a, 2a, 2b, or 3a, such as lithium, sodium, beryllium, barium, boron, aluminium, zinc, cadmium, and gallium, and k equals 1, 2, or 3, By the valence of M3 which in turn usually depends on the specific group to which M3 belongs; Each R3 represents any monovalent hydrocarbon moiety.

Examples of conventional-type organometallic co-catalysts of Groups 1a, 2a, and 3a that are suitable for use with the conventional-type catalytic complexes described above include, but are not limited to, methylthium, butyllithium, dihexylmercury, butylmagnesium, diethylcadmium, benzylpotassium, diethyl zinc, and tert-P. -Aluminium-butyl, diisobutylethylboron, diethyl cadmium, and di-A-butyl zinc and tri-A-Amylboron, especially aluminum alkylates such as trihexyl aluminum, triethyl aluminum, and triethyl aluminium. Aluminum and triisobutyl aluminum. Other conventional type co-catalyst compounds include single-radical organic halides and group 2a metal hydrides, and single- or double-radical organic halides and group 3a metal hydrides. Examples include

Co-catalytic compounds of a conventional type such as, but not limited to, bromide

Aluminum diisobutyl, isobutylboron dichloride, methylmagnesium chloride, ethyl beryllium chloride, ethyl calcium bromide, diisobutyl aluminum hydride, methylcadmium hydride, diethylboron hydride, hexyl beryllium hydride, dipropylboron hydride, magnesium octyl hydride, zinc butyl hydride, dichloroboron hydride, dibromoaluminum hydride

Bromocadmium hydride. Conventional organometallic co-catalysts are well known to those familiar with the technology, and a fuller description of these compounds is provided in US Patent Nos. 3,221,002 and 5,093,415, which are fully incorporated into this statement for reference.

For the purpose of this description and the appended claims, conventional type transition metal catalyst compounds exclude those metallocene catalytic compounds containing the bulky ligand described below. For the purposes of this description and the appended claims, the term “co-catalyst” when used in this Statement refers to conventional type co-catalysts or conventional type organometallic co-catalyst compounds. Compounds and catalytic systems of the metallocene type containing a bulky ligand for use in combination with a metal carboxylate salt in accordance with this invention are described below.

Metallocene-type catalytic compounds containing a bulky ligand

Metallocene-type catalytic compounds containing a bulky ligand generally include semi- and full-layer compounds containing one or more bulky ligands, including cyclopentadienyl or other similar functional structures such as pentadiene, cyclooctatradieneyl, and imides. In general, typical metallocene-type compounds containing a bulky ligand are described as containing one or more ligands that have the ability to bind to a transition metal atom with an ETA bond at position 5, usually ligands or moieties derived from a cyclopentadienyl in combination with a transition metal chosen from groups 3 to 8. Groups 4, 5, 6, or from the lanthanide and actinide series of the periodic table of elements are preferred. These examples have been described for compounds

Metallocene catalytic systems containing a bulky ligand and catalytic systems, for example, in US patents Nos. 4,530,914, 4,871,705, 4,937,299, 5,017,714, 5,055,438, and 5 096,867, 5,120,867, 5,124,418 and

5,198,401, 5,210,352, 5,229,478, 5,264,405, 5,278,264 and

5,278,119, 503,040,614, 5,324,800, 5,347,025, 5,350,723 and

5,384,299, 5,391,790, 5,391,789, 5,399,636, 5,408,017 and

5,491,207, 5,455,366, 5,534,473, 5,539,124, 5,554,775 and

5,621,126, 5,684,098, 5,693,730, 5,698,634, 5,710,297 and

5,712,354, 5,714,427, 5,714.88, 5,728,641, 5,728,839 and

5,753,577, 5,767,209, 5,770,753, and 5,770,664, all of which are fully incorporated herein by reference. Also, all of the following patents have been fully incorporated by reference for purposes of describing metallocene compounds and catalytic systems containing a bulky ligand, namely European Patents Nos. 0-591-756 A-, 0-485-732 A-436, 0-420-436, B1-0 485-822 and 0-485-823. B1, 0,743,324 -A2, 0, 518,092 B1 and PCT International Patent Bulletins Nos. 91/04257, 92/00333, 93/08221, 93/08199, 94/01471, 96/20233 and 97/15582 97/19959, 97/46567, 98/01455, 98/06759 and 98/011144.

In an embodiment of the invention, metallocene-type catalyst compounds containing a bulky ligand according to the invention are represented by the formula:

LALBMQ (1)

Where M is a metal chosen from the periodic table of elements, and may be chosen from groups 3 to 10. It is preferable for it to be a transition metal from group 4, 5, or 6, or a metal chosen from the lanthanide or actinide series. It is preferable for M to be a transition metal chosen from group 4, and preferably zirconium. Or hafnium or titanium. LA and LB represent bulky ligands that include ligands

A derivative of a cyclic penta-dienyl or ligands A derivative of a cyclic penta-dienyl containing a heteroatom or ligands A derivative of a cyclic penta-dienyl containing a heteroatom or carrying a substitute thereof or ligands A derivative of a cyclic penta-dienyl carrying a hydrocarbyl substituent or moieties such as indienyl ligands, benzenedyl ligands, fluorenyl ligands and ligands Octahydrofluorenyl, cyclic octatriandyl ligands, aznyl ligands, borabenzene ligands and the like, including their hydrogenated forms. LA and LB may also represent any other bond structure that has the ability to bond with M eta bond at position 5, for example LA and LB contain one or more heteroatoms, e.g.

Nitrogen, silicon, boron, germanium and phosphorus combine with carbon atoms to form a structure

Cyclocyclic, for example an additional cyclic pentadienyl ligand. In addition, LA and LB may also represent other types of bulky ligands including, but not limited to, amides, phosphides, alkoxides, aryloxides, imides, carbolides, borolides, porphyrins, phthalocyanines, bulky corines and other macrocyclic polyazo. Both LA and LB represent identical or different types of bulky ligand bound to the A-linked π-link.

LA and LB may each have a substituent from a combination of R groups. Examples of R substituents include, but are not limited to, hydrogen, linear or branched alkyl moieties, cyclic alkyl moieties, alkenyl, alkynyl, aryl moieties, or combinations thereof containing from 1 to 30 A carbon atom or other substituent containing no more than 50 atoms other than hydrogen can also carry substituents. Examples of R alkyl substituents include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl groups, halogens and the like, including all blue ones, for example tert-butyl and isopropyl. ..etc. Other hydrocarbyl radicals include semi-metallic organic radicals bearing a fluoromethyl substituent

Fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl, including

Including trimethylsilyl, trimethylgermyl, dimethylsilyl, and the like, and semi-metallic organic moieties bearing a halocarbyl substituent, including tri(trifluoromethyl)-silyl, methyl-di(difluoromethyl)silyl, bromomethyldimethylsilyl, and the like. That and flats

Disubstituted boron including, for example, dimethylboron, disubstituted pectogen moieties including dimethylamine, dimethylphosphine, diphenylamine, and methylphenylphosphine, and chalcogen moieties, including methoxy, ethoxy, propoxy, phenoxy, methyl sulfide, and ethyl sulfide. Non-hydrogen R substituents include carbon, silicon, nitrogen, phosphorus, oxygen, tin, germanium and the like, including but not limited to olefins. Unsaturated olefin substituents include phenyl terminal ligands, for example butenyl (3), 2-phenyl, or hexene (1). Also, at least two R groups, and preferably two adjacent R groups, are linked to form a ring structure containing from 4 to 30 atoms selected from carbon

Or nitrogen, oxygen, phosphorus, silicon, germanium, boron, or a combination

Of which. Also, an R group, such as 1-butanyl, may form a sigma bond with the metal M.

Other ligands may bind to the transition metal, such as an easily removable group symbolized by Q.

where Q may individually represent an unstable monoanionic ligand linked to M a sigma bond. Examples of Q include, but are not limited to, weak bases such as amines, phosphines, ethers, carboxylate compounds, dienes, hydrocarbyl radicals containing from 1 to 20 carbon atoms, hydrides, halogens, and the like, and combinations thereof. Other examples of Q moieties include the alternatives mentioned above for the R moiety described above and include cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylenemethylidene, methoxy, ethoxy, propoxy, phenoxy, di(N-methylanilide), di(N-methylanilide), di-shell amide, dimethylphosphide, and the like.

In addition, the metallocene-type catalytic compounds containing a bulky ligand according to the invention include those where LA and LB represent two moieties bridged together by a bridge group symbolized by A. These bridged compounds are known as metallocene-type bridge catalytic compounds containing On a huge bundle. Examples of bridge group A include, but are not limited to, bridge moieties selected from at least one of the group 14 atoms, such as, but not limited to, carbon, oxygen, nitrogen, silicon, germanium, tin, preferably carbon, silicon, germanium, and most preferably

Silicone. Examples of other A bridge groups include, but are not limited to, dimethylsilyl, diethylsilyl, ethylsilyl, trifluoromethylbutylsilyl, di(trifluoromethyl)silyl, di-p-butylsilyl, cyclobutylsilyl, di-iso-propylsilyl, and dihexylcyclosilyl. Silyl, diphenylsilyl, cyclohexyl phenylsilyl, tributylcyclohexyl, silyl, dithylsilyl, phenylsilyl, 2-(para-tolyl) silyl, dimethylgermyl, diethylgermyl, methylene, dimethylene, diphenylmethylene, ethylene, 1,2-methylethylene, 1,2- Diphenylethylene And 1,1,2,2-tetramethylethylene, dimethylethylethyl, dimethylsilyl, diphenylgermyl, methylamine, phenylamine, methylcyclohexylamine, methylphosphine, phenylphosphine, hexylcyclophosphine, and the like.

In another embodiment, the metallocene-type catalytic compound containing a bulky ligand according to the invention is represented by the formula:

C5H4-dRd)Ax(C5H4-dRd)MQg-2) (2)

Where M supplies a transition metal selected from groups 4, 5, and 6, and (C5H4-dRd) represents a bulky ligand derived from a cyclopentadienyl with or without substituents attached to M, and each R, which may be the same or different, supplies a hydrogen atom or a substituent group containing not more than 50 non-hydrogen or hydrocarbyl atoms bearing or devoid of substituents Containing from 1 to 0 3 carbon atoms or combinations thereof, or two or more carbon atoms bonded to each other to form part of a ring or system Ring bearing or devoid of substituents Containing 4 to 30 carbon atoms , and A represents a radical containing one atom or More or a combination chosen from carbon, germanium, silicon, tin, phosphorus, or nitrogen, connecting two rings of (C5H4-dRd) bridgely. More specifically, examples may represent A, but are not limited to R′2C, R′2Si, R′2SiR′2Si, and R. ′2SiR′2C, R′2Ge, R′2iR′2Ge, R2GeR2C, R′N, R′P, R′2CR′N, R′2CR′P, R′2SiR′N, R′2SiR′P, R′ or Semi-metallic organic compound

A halocarbyl substituent, a disubstituted boron, a bisubstituted pentogen, a chalcogen bearing a substituent, or a halogen. Each Q, which may be the same or different, represents a linear, cyclic, or branched hydride or hydrocarbyl bearing or devoid of substituents, containing from 1 to 30 carbon atoms, or Halogens, alkoxides, aryloxides, amides, phosphides, or any other monovalent anionic ligand, or a combination thereof, and two Q groups may also form an alkylidene ligand, a cyclic metal hydrocarbyl ligand, or another divalent anionic chelating ligand, where g is an integer It represents the formal oxidation state of M, and d represents an integer chosen from 0, 1, 2, 3, or 4 and represents the degree of substitution, and x represents an integer equal to 0 or 1.

In an embodiment of the invention, metallocene-type catalytic compounds containing a bulky ligand include those where the R substituents on the bulky ligands LA, LB and (C5H4-dRd) of formulas (1) and (2) carry a similar or different number of substituents on each of the ligands Huge.

In a preferred embodiment, a metallocene-type catalyst containing a bulky ligand is given by formula (2), where x equals 1.

Other catalyst compounds of the metallocene type that contain a bulky ligand and are suitable for use in this invention include bridge compounds of the metallocene type that contain a heteroatom and a single bulky ligand. Examples of these catalytic types and catalytic systems are described, for example, in PCT International Patent Publications Nos. 92/00333, 94/07928, 91/04257, 94/03506, 96/00244, and 97/15602, and US Patent Nos. 5,057. 475, 5,096,867, 5,055,438, 5,198,401, 5,227,440, and 5,264,405 and European Patent Publication No. 436 420 0 A-, all of which are fully incorporated herein by reference. to it for reference. Other metallocene catalysts that contain a bulky ligand and are suitable for use in this invention are those described in US Patent Nos. 5,064,802, 45,819, 5.1, 5,149,819, 5,243,001, 5,239,022, and 5,276,208, 5,296,434, 5,321,106, 5,329,031 and

5,304,614, 5,677,401 and 5,723,398, PCT International Patent Bulletins Nos. 93/08221, 93/08199, 95/07140, 98/11144 and European Patent Bulletins Nos. A-0578 838 and 595 638 0-A, 380 513 B-0 and 372 6 81 A1-0, all of which are incorporated into this statement by reference.

<img file="SA938B1_D0001.tif" />

In another embodiment according to this invention, bridge catalyst compounds of the metallocene type containing a heteroatom and a single bulky ligand that are suitable for use in this invention are represented by the formula:

where M supplies Ti, Zr, or Hf; (C5H5-y-xRx) represents a ring or ring system of cyclopentadienyl containing from 1 to 5 substituent groups R, and &amp; x &amp; equals 0, 1, 2, 3, 4, or 5, which represents the degree of substitution, and each substituent R represents a radical. It is chosen from a class consisting of hydrocarbyl radicals containing from 1 to 20 carbon atoms, hydrocarbyl radicals with substituents containing from 1 to 20 carbon atoms, where one or more hydrogen atoms are replaced by a halogen atom, or semi-metallic radicals bearing a hydrocarbyl substituent containing from 1 to 20 carbon atoms. He chooses the semi-metal from the elements in group 14 of the table Cyclic elements or halogen moieties or (C5H5-y-xRx) represents a cyclic pentadienyl ring in which two adjacent R groups are linked to form a ring containing from 4 to 20 carbon atoms to produce a saturated or unsaturated polycyclic cyclic pentadienyl ligand.

such as indenyl, tetrahydroindyl, fluorenyl, or octahydrofluorenyl;

And (JRz-1-y) supplies a ligand containing a heteroatom, where J supplies an element with a coordination number of 3, chosen from group 15 of the periodic table of elements, or an element with a coordination number of 2, chosen from group 16 of the periodic table of elements, preferably nitrogen, phosphorus, or oxygen. Or sulfur, where nitrogen is the most preferred and each ′R separately represents a moiety

Choose from the class consisting of hydrocarbyl radicals containing from 1 to 20 carbon atoms, where one or more hydrogen atoms are replaced by a halogen atom, y equals 0 or 1, and &amp;z&amp; represents the coordination number of the element J;

Each individual Q represents a monovalent anionic ligand such as a halogen, hydride, or...

Hydrocarbyl contains from 1 to 30 carbon atoms, with or without substituents, alkoxides, or...

An aryloxide, amide or phosphide, provided that two Q groups represent an alkylidene moiety, cyclic metal hydrocarbyl or other divalent anionic chelating ligand and n may equal 0, 1 or 2; A represents a covalent bridge group containing an element chosen from group 15 or 14 of the periodic table of elements, such as, but not limited to, a dialkyl, alkyl aryl, diaryl silicon or germanium moiety, an alkyl or aryl phosphine, an amine, or a hydrocarbyl moiety such as methylene, ethylene, and the like. that;

It includes a Lewis base such as diethyl ether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, p-butylamine, and the like, and w represents a number ranging from 0 to 3. In addition, ′L may be associated with any of the slots R, ′R, or Q, and n equals 0, 1, 2, or 3.

In another embodiment, the catalytic compound is a metallocene type containing a bulk ligand that is a complex of a transition metal and a ligand bound to a Pi bearing or devoid of substituents and one or more allele moieties such as those described for example in U.S. Pat. No. 5,527. 752 and 5,747,406 and European Patent 057 735 B1-0, all of which are incorporated into this statement by reference. The metallocene catalytic compound containing a bulky ligand, i.e. a monocyclic alkadienyl catalytic compound, is preferably represented by one of the following two formulas:

<img file="SA938B1_D0002.tif" />

Where M represents a transition metal chosen from groups 4, 5, or 6, preferably titanium or

Zirconium or Hafnium and most preferably Zirconium or Hafnium; L represents a ligand bound to any substituent that is devoid of it. It is symmetrically linked to M. It is preferable for L to represent a bulky ligand of cyclic alkadienyl, for example bulky ligands of cyclopentadienyl, indenyl, or fluorenyl, and it is permissible with one or more hydrocarbyl substituent groups containing from 1 to 20. carbon atom; Each individual Q chooses from the class consisting of -O-, -NR-, -CR2-, and -S-, preferring oxygen; Y represents C or S, preferably carbon, and Z is chosen from the category consisting of OR-, NR2-, CR3-, and SR-. SiR3, PR2-, H- and aryl groups have or do not have substituents, provided that when representing NR-Q-, z is chosen from the class consisting of OR-, NR2-, SR-, SiR3, PR2- and H-, preferably choosing z. Of the category consisting of OR-, CR3-, and NR2-, n equals 1 or 2, preferably 1; A represents a monovalent anionic group when 11 equals 2, or A represents a divalent anionic group when 11 equals 1. Preferably, A represents a carbamate or carboxylate moiety or any other heteroallelic moiety described for the Q, Y, and Z moiety. Each R represents a

Unit of a group containing carbon, silicon, nitrogen, oxygen, and phosphorus.

Whereas one or more R groups may be attached to the L-substituent, preferably the R represents a hydrocarbon group containing from 1 to 20 carbon atoms, and most preferably an alkyl, cycloalkyl, or aryl group, and one or more groups may be attached to the L-substituent; T represents a bridge group chosen from the class consisting of an alkylene and arylene group containing from 1 to 10 carbon atoms, which may carry a substituent of carbon or one or more heteroatoms, germanium, or silicon, and the alkyl phosphine, and m represents a number ranging from 2 to 7, preferably from 2 to 6. The most preferable is 2 or 3.

In formulas (4) and (5) the auxiliary substituent formed by the Q, Y and Z groups is a single-charge polydentate ligand that exerts electronic effects due to its high polarizability, similar to the cyclopentadienyl ligand. In most preferred embodiments of this invention, disubstituted carbamates and carboxylates are used. Examples of these compounds include catalytic compounds

Of the type of metallocene, which contains bulky ligands, including, but not limited to, tri-(diethyl carbamate) indenylzirconium, tri-(tri-acetate) indenylzirconium, tri-(para-tolate) indenylzirconium, tri-(benzoate) indenylzirconium, and tri-(tri-methyl acetate). ) (1-methylindenyl)zirconium and tri-(diethyl carbamate) (2-methylindenyl)zirconium and tri-(trimethyl acetate) (cyclopentadienyl methyl) zirconium and tri(trimethyl acetate) cyclopentadienyl and tri(trimethyl acetate) Tetrahydroindylzirconium and tri(benzoate) (v Cyclopentadienyl methyl zirconium. Preferred examples include tri(diethylcarbamate)indenylzirconium, tri(trimethylacetate)indenylzirconium, and tri(trimethylacetate) (methyl

Cyclopentadienyl)zirconium.

In another embodiment of the invention, metallocene-type catalyst compounds containing a bulky ligand include those nitrogen-containing mixed cyclic ligand complexes, also known as transition metal catalysts based on double-dented ligands containing pyridine or quinoline moieties, such as those described in international patent application publications Nos. 96/33202, 99/01481, 98/42664, and US Patent No. 0 5,637.66, all of which are incorporated herein by reference.

Within the scope of one embodiment of this invention, Ni2+ and Pd2+ composites of a metallocene-type catalytic compound containing a bulky ligand described in the articles by Johnson and his associates entitled &amp; New Palladium(2) and Nickel(2)-Based Catalysts for the Polymerization of Ethylene and Alpha-Olefin Compounds can be combined. In the Journal of the American Chemical Society, vol. 117, pp. 6414-6415, 1995, Johnson and his co-authors entitled &amp; Copolymerization of Ethylene and Propylene with Vinyl Functional Monomers Using Palladium Catalysts (2), in the Journal of the American Chemical Society, vol. 118, p. 267- 268, 996 1 and International Patent Application Bulletin No. 96/23010 issued on August 1, 1996, all of which are incorporated herein by reference, combined with a metal carboxylate salt for use in the process in accordance with this invention. These complexes may be either addition products of dialkyl ethers or alkylation reaction products of the dihalide complexes

which can be activated to a cationic state by the use of conventional type co-catalysts or activators in accordance with this invention which will be described below.

Likewise, metallocene-type catalytic compounds containing a bulky ligand include those binary amine-based ligands of metal compounds of complexes 8 to 10 described in PCT International Patent Application Bulletins Nos. 69/2301 and 97/48735 and in the Journal of the Chemical Society in the name of Gibson And those with him, pp. 849-850 (1998), all of which have been incorporated into this statement for reference.

The metallocene-type catalyst and other bulky ligand compounds include those imide complexes of group 5 and 6 metals described in European Patent 384,816 0-A2 and US Patent 5,851,945, which are incorporated herein by reference. In addition, metallocene-type catalysts containing a bulky ligand include bridge compounds of a selected group IV metal di(willamido) described by D. H. McConville and others in the Journal of Organometallic Compounds, Volume 1195, Issue 14, pp. 5478-5480, which is incorporated into this statement by reference. Other metallocene catalysts containing a bulky ligand in dimer form (hydroxylated aromatic nitrogen ligands) are described in US Pat. 46 5.852.1, which is incorporated into this statement by reference. Other metallocene-type catalysts containing one or more atoms from Group 15 of the periodic table of elements include those described in International Patent Publication No. 98/46651, which is incorporated herein by reference. Other metallocene-type catalysts that contain a huge ligand include multinucleated metallocene-type catalysts that contain a huge ligand as described in International Patent Publication No. 99/20665, which has been incorporated into this statement for reference.

It is understood that in some embodiments, the bulky ligands of the metallocene catalytic compounds of the present invention described above may be asymmetrically substituent

Where the additional substituents or types of substituents are unbalanced in terms of the number of additional substituents present on the bulky ligands or the bulky ligands themselves are different.

It is also understood that in one embodiment, the metallocene-type catalysts containing a bulky ligand according to the invention include their structural or photonic groups or dispersals (meso and racemic groups) and mixtures thereof. In another embodiment, the metallocene-type compounds containing a bulky ligand according to this invention may be chiral and/or a metallocene-type catalytic compound containing a bulky ligand.

The activator and activation methods used to prepare metallocene-containing catalytic compounds

Huge bond

Catalytic compounds of the metallocene type containing the bulky ligand described above according to the invention are usually activated in several ways to produce catalytic compounds having a free coordination site where

It coordinates and polymerizes one or more fibrins.

For the purpose of this description and the appended claims, the term “comb” when used in this statement means any compound, component or method that can activate any metallocene-type catalytic compound containing a bulky ligand in accordance with the invention as described above. These activators may include, but are not limited to, a Lewis acid, a non-coordinated ionized activator, an ionized activator, or other compounds including Lewis bases, aluminum alkyls, conventional type co-catalysts (mentioned previously in this statement) and combinations thereof that can convert the neutral catalytic compound to Metallocene containing a bulky ligand to a catalytically active cation of the type metallocene containing a bulky ligand. Within the scope of this invention, almoxane or modified almoxane may be used as a stimulant, and/or ionizing stimulants may also be used, whether neutral or ionic such as tetra(pentafluorophenyl)boron tri(p-butyl)ammonium or a semi-metallic precursor of trifluorophenylboron or A semi-metallic precursor of trifluoronaphthylboron or its anions

A mixed polyhydrogen borane (see International Patent Publication No. 98/43983) or a combination thereof that may ionize into a neutral metallocene compound containing a bulky ligand.

In an embodiment of the invention, an activation method employing ionized ionic compounds devoid of a functional proton but capable of producing both a catalytic catalytic cation of the metallocin type containing a bulky ligand as well as a non-coordinating anion is also used and is described in European Patents 637 426 0-A and 403 573 A- 0 and US Patent 5,387,568, which is incorporated into this statement by reference.

There are various methods for preparing almoxane and modified almoxane compounds, including, but not limited to, those described in US Patent Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, and 5,204,419. 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5. 157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656 and European Patent Bulletin Nos. 476 561 0 A-, 586 279 B1-0 and 594218 A-0 and the International Patent Application Bulletin in accordance with the Treaty on Cooperation in Patent field No. 94/10180, all of which are fully incorporated into this statement for reference.

Ionized compounds may contain an active proton or some other cation that is bonded to the remaining ion in the ionized compound, but is not coordinately bonded to it at all, or is bonded to it only to a small degree. Compounds of this type and similar ones are described in European Bulletins No. 982 570 A-0 and 732 520 A. -0, A-0495,375, A-0 500,944, 330,277 A-0, A-277004, and US Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299, and 5,502,124. U.S. Patent Serial No. 08/285,380, filed on August 3, 1994, has been incorporated All of them are fully included in this statement for reference.

Other activators include those described in the International Patent Publication pursuant to PCT No. 98/07515, such as tri(2,2,2-nonafluorodiphenyl)fluoroalamines, which are fully incorporated into this Statement by reference.

The invention also uses different combinations of stimulants, for example almoxane compounds and ionized stimulants in combination. Consider, for example, the European Patent 25 5731 0 Bl, the two International Patent Cooperation Treaty Patent Publications Nos. 94/07928 and 95/14044, and the American Patent Nos. 5.153. 157 and 5,453,410, all of which are fully incorporated into this statement by reference. International Patent Publication No. 98/09996, which is incorporated into this statement for reference, describes the activation of metallocene-type catalytic compounds containing a bulky ligand using perchlorate, periodate, and iodate compounds, including their aqueous forms. International Patent Publications Nos. 98/30602 and 98/30603, which are incorporated into this statement by reference, describe the use of (2,2-diphenyl-ditrimethyl silicate) for thiium. 4THF as an activator for metallocene-type catalytic complex containing bulky ligand. International Patent Publication No. 99/18135, incorporated into this statement for reference, describes the use of organic boron and aluminum activators. European Patent 299 781 0-Bl describes the use of a silium salt combined with a non-coordinating anion. Likewise, the invention also uses methods such as radiation (see European Patent 981 615 0-Bl which is incorporated herein by reference), electrochemical oxidation and the like as activation methods to achieve the purposes of making a metallocene-type catalyst compound or precursor containing a bulky ligand neutral. Or a metallocene-type cation containing a bulky ligand capable of polymerizing olefins. Doping or other methods for activating a metallocene catalytic compound containing a bulky ligand are described in US Patent Nos. 5,849,852 5,859,653 5,869,723 and PCT International Patent Application Publication No. 98/32775, which is incorporated herein For reference.

Mixed catalysts

It is also within the scope of this invention that metallocene-type catalyst compounds containing a bulky ligand can be combined with one or more of the represented catalyst compounds.

In formulas (1), (2), (3), (4) and (5) using one or more activators or activation methods of one or more of the activators and methods described above.

It is also realized in this invention that it is possible to combine other catalysts with metallocene-type catalyst compounds that contain a bulky ligand according to the invention. Consider, for example, US Patent Nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241, all of which are fully incorporated into this statement for reference.

for reference.

In another embodiment of the invention, one or more catalytic compounds or systems of a metallocene type containing a bulky ligand may be used in combination with one or more catalytic compounds or systems of a conventional type. Non-specific examples of mixed catalysts and mixed catalyst systems are described in US Patents 4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, and 5,183,867. 5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031 and PCT International Patent Application Bulletin No. 96/23010 of August 1, 1996, All of these bulletins have been fully incorporated into this statement for reference.

It is also recognized that two or more conventional type transition metal catalysts may be combined with one or more conventional type co-catalysts. Conventional mixed-type transition metal catalysts are described, but are not limited to, in US Patents 4,154,701, 4,210,559, 4,263,422, 4,672,096, 4,918,038, and 5,198. 4, 5,237,025, 5,408,025, and 5,420,090, all of which are incorporated into this statement by reference.

Methods of carrying the catalyst

Mass ligand-containing metallocene-type catalyst compounds and systems and conventional-type transition metal catalyst compounds and systems may be combined with one or more support or carrier materials or carriers using one of the catalyst loading methods well known in the art or

As will be described below. In a preferred embodiment, the method of this invention uses a polymerization catalyst in a portable form. For example, according to the most preferred embodiment, the catalyst or catalytic system is of a metallocene type containing a bulky ligand in a mobile form, e.g., deposited on, in contact with, or embedded in a distinct or adsorbed support or carrier.

The terms “support” or “carrier” when used interchangeably in this statement mean any porous or non-porous support material, preferably a porous support material, for example talc, inorganic oxides, and inorganic chlorides. Other carriers include resinous support materials such as polystyrene, functional or cross-linked organic supports such as polystyrene, divinylbenzene, polyolefins, polymeric compounds, other organic or inorganic support materials and the like, or mixtures thereof.

The preferred carriers are inorganic oxides, including those metal oxides of groups (2), (3), (4), (5), (13), or (14) of the periodic table of the elements.

Preferred substrates include silica, enamel, silica-almina, magnesium chloride, and mixtures thereof. Other useful binders include magnesia, titania, zirconia, montmorillonite and the like. It is also possible, for example, to use combinations of these supporting materials, for example silica-chromium and silica-titania.

The carrier, which is preferably an inorganic oxide, should preferably have space

Surface in the range from about 10 to about 700 m2/g and pore space in the range from about 0.1 to about 4 cm3/g and average particle size in the range from about 10 to about 500 micrometers. Ideally, the surface area of the carrier should range from about 50 to about 500 m2/g and its pore volume should range from about 0.5 to about 3.5 cm3/g

Its average particle size ranges from about 20 to about 200 micrometers. It is most preferable for the surface area of the carrier to range from about 100 to about 400 m2/g, its pore volume to range from about 0.8 to about 3 cm3/g, and its average particle size from about 20 to about 100 micrometers. The average pore size of the carrier material usually varies according to the invention

From about 10 angstroms to 1000 angstroms, preferably from 50 angstroms to about 500 angstroms, and most preferably from 75 angstroms to about 350 angstroms.

Examples of metallocene catalytic systems containing a bulky ligand are described in accordance with the invention in US Patent Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, and 5. 0080,228, 5,238,892, 5,240,894 and

5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766 and

5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835 and

5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424.

5,723,400, 5,723,402, 5,731,261, 5,759,940, 5,767,032 and

5,770,664, US patent application serial number 271,598 filed on July 7, 1994 and serial number 788,736 filed on January 23, 1997, and PCT International Patent Application Bulletins Nos. 95/32995, 95/4044, 96/06187, and 97 /02297, all of which are fully incorporated into this Statement by reference.

Examples of carrying conventional type catalytic systems according to the invention are described in US Patent Nos. 4,894,424, 4,376,062, 4,395,359, 4,379,759, 4,405,495, 4,540,758, and 5 096,869, all of which are incorporated herein by reference.

It should be understood that metallocene-type 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 a non-loaded form, or it may be deposited on a different support than metallocene-type catalyst compounds containing a bulky ligand According to the invention or any combination thereof.

There are various other methods in the technology for carrying a polymerization compound or catalytic system according to the invention.

For example, a metallocene-type catalyst containing a bulky ligand according to the invention may contain a ligand bound to a polymer as described in U.S. Pats 5,473,202 and 5,770,755, which are incorporated herein in their entirety by reference, which The metallocene catalytic system containing a bulky ligand according to the invention is dried by spray drying as

Described in US Patent 5,648,310, which is fully incorporated herein by reference, the carrier used with a metallocene-type catalytic system containing a bulky ligand according to the invention contains functional groups as described in European Publication 203 802 0 -A , which are incorporated herein in their entirety by reference; Or select an alternative or easy-to-remove assembly as described in U.S. Pat. No. 5,688,880, which is incorporated herein in its entirety by reference.

In a preferred embodiment, this invention provides a portable metallocene catalytic system containing a bulk ligand including a surface modifier used in the preparation of the portable catalytic system, as described in the International Publication pursuant to PCT No. 96/11960, which is fully incorporated herein For reference.

A preferred method for producing a portable metallocene catalytic system containing a bulk ligand in accordance with the invention will be described below and can be found in the US patent applications, serial number 265,533, filed on June 24, 1994, and serial number 265,532, filed on June 24, 1994, and the two international patent publications in accordance with the Treaty. In the field of patents Nos. 96/00245 and 96/00243, issued on January 4, 1996, all of which are fully incorporated into this statement for reference. In this preferred method, the metallocene catalytic compound containing the bulk ligand is slurred in a liquid to form a metallocene solution and a separate solution is formed containing the activator and liquid. The liquid may be a homogeneous solvent or any other liquid capable of forming a solution or the like with metallocene-type catalyst compounds containing a bulky ligand and/or activator according to the invention. In the most preferable embodiment, the liquid is an aliphatic or cyclic aromatic hydrocarbon, most preferably toluene, and a solution of the metallocene catalytic compound containing the bulky ligand and the activator is mixed together and added to a porous support or the porous support is added to them such that the total pore space of the solution of the catalytic compound is of the type Metallocene, which contains a bulky ligand, as well as an activator solution or catalytic compound of the type of metallocene, which 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 absolute best is less than three times, with the preferred ranges ranging from 1.1 to 3.5 times, and the most preferred ranges from 1.2 to 3 times.

Procedures for measuring the total pore space of a porous support are known in the technique. The details of one such procedure are presented in a book entitled Experimental Methods in Catalytic Research (Academic Press, Inc., 1968), Volume 1, specifically pages 67-96. This preferred procedure involves the use of a conventional nitrogen adsorption device according to the Brunaroimt and Teller method. Another well-known method of the technique was described in the article entitled Total Porosity and Total Particle Density of Catalyst Fluids by Liquid Titration, Ins., Vol. 28, No. 3 in Analytical Chemistry, pp. 332-334, (March, 1956).

The molar ratio of the metal of the activated component to the metal of the metallocene catalytic compounds that contain a bulky ligand ranges from 0.3:1 to 1:2000, preferably from 1:20 to 800:1, and most preferably from 1:50 to 1:500. When the activator is an ionized activator, such as one based on the tetra(pentafluorophenyl)boron anion, it is preferable that the molar ratio of the activating component metal to the catalyst metal component range from 0.3:1 to 1:3.

In one embodiment of the invention, one or more olefins, preferably one alpha-olefin, are polymerized

or more containing from 2 to 30 carbon atoms, preferably ethylene or propylene or combinations thereof, in

The presence of a metallocene catalytic system containing bulk ligand and/or transition metal catalysts of a conventional type according to the invention prior to the core polymerization. Prepolymerization can be carried out in an intermittent or continuous manner in a gas, solution or slurry phase and under high pressures. The prepolymerization may be performed using any olefin monomer or combination and/or in the presence of any molecular weight control agent such as hydrogen. For examples of prepolymerization procedures, see US Patent Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278, and 5,705,578 and the European Patent Bulletin. 863 279 A-0 and the International Patent Bulletin pursuant to PCT No. 97/44371, all of which are incorporated into

This statement is made entirely for reference. The pre-polymerized catalytic system for the purpose of this description and the attached protective elements shall be a portable catalytic system.

Metal carboxylate salt

Metal carboxylate salts are well known in technology as additives for use with polyolefins, for example as film treatment adjuvants. These kinds of post-treatment additives are usually used in the reactor as emulsifying agents, antistatic agents, anti-fogging agents, stabilizers, foaming agents, lubricating agents, anti-adhesion agents, nucleating agents, sliding agents, anti-caking agents and the like. Thus, it was not really expected that these agents or post-reactor catalysts would be useful in combination with a polymerization catalyst to improve the workability of the polymerization process.

For the purposes of this description and the appended claims, the term “carboxylate salt of a metal” when used in this Statement means a salt of a mono-, di-, or tri-carboxylic acid with a metal element from the periodic table of the elements. Examples include, but are not limited to, saturated, unsaturated, aliphatic, aromatic, or cyclic carboxylic acid salts, where the carboxylate ligand preferably contains from 2 to 24 carbon atoms, such as acetate, propionate, butyrate, valerate, pivalate, caproate, isobutyl acetate, th-butyl acetate, caprylates, and heptanes. Pelargonate, undecanoate, oleate, octanoate, palmitate, myristate, margarate, stearate, arachate, and nercosanoate. Examples of a metal element include, but are not limited to, a metal from the periodic table of elements chosen from the class consisting of A1, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li, Na.

In an embodiment, the metal carboxylate salt is represented by the following general formula

M(Q)x(OOCR)y

Where M represents a metal chosen from groups 1 to 16 of the lanthanide and actinide series, preferably from

Groups 1 to 7 and 13 to 16, and the best of the groups 3 to 7 and 13 to 16, and the most preferable are groups 2 and 13, and the absolute best is group 13, and Q represents halogen or

Hydrogen, hydroxy, hydroxide, alkyl group, alkoxy, aryloxy, or

Siloxy, silane, or silane sulfonate, and R represents a hydrocarbyl radical containing from 2 to 100 carbon atoms, preferably 4 to 50 carbon atoms, and x represents an integer ranging from 0 to 3, and y represents an integer ranging from 1 to 4, so that the sum of x and y equals Valence of the metal. In a preferred embodiment of the formula shown above, y represents an integer ranging from 1 to 3, preferably from 1 to 2, especially when M represents a group 13 metal.

Examples of group R in the above formula represent, but are not limited to, flats

Hydrocarbyls containing from 2 to 100 carbon atoms including alkyl, aryl, or hydrocarbyl moieties.

Saturated or unsaturated, aromatic, aliphatic, or cyclic. In one embodiment of the invention, R represents a slit

Hydrocarbyl contains 8 or more carbon atoms, preferably 12 or more carbon atoms, and preferably 17 or more carbon atoms. In another embodiment, R represents a hydrocarbyl moiety containing from 17 to 90 carbon atoms, preferably from 17 to 72 carbon atoms, and most preferably from 17 to 54 carbon atoms.

carbon.

Examples of Q in the formula shown above include, but are not limited to, a group containing one or more identical or dissimilar hydrocarbons such as an alkyl, cycloalkyl, aryl, alkenyl, aryl alkyl, aryl alkenyl, alkyl aryl, alkyl silane, aryl silane, alkyl amine, or Aryl amine, alkyl phosphide, or alkoxy, contains from 1 to 30 carbon atoms. The group containing a hydrocarbon may be linear, branched, or even carry substituents. Also, Q in one embodiment may represent an inorganic group such as a halide, sulfate, or phosphate.

In an embodiment, the more preferable metal carboxylate salts include such aluminum carboxylate compounds as first, second and third aluminum stearate compounds and octoate, oleate and cyclohexyl aluminum butyrate compounds. In a more preferable embodiment the metal carboxylate salt may also be CH3(CH2)16COO)3Al), i.e. a third aluminum stearate (preferred melting point of 115 dM) and CH3(CH2)16COO)3Al-OH), i.e. a second Aluminum stearate

(Preferred melting point is 145°C) and CH3(CH2)16COO)3Al), the first stearate

Aluminum (preferred melting point is 155 dm).

Commercially available metal carboxylate salts include, but are not limited to, Whitco Aluminum Stearate No. 18, Whitco Aluminum Stearate No. 22, Whitco Aluminum Stearate No. 132, and Whitco Aluminum Stearate EA Food Grade, all available from Whitco Corporation, Memphis, Tennessee.

In one embodiment, the melting point of the metal carboxylate salt ranges from about 30 to about 250 to most preferably from about 37 to about 220 to most preferably from about 50 to about 200 to most preferably. From about 100 Dh. to about 200 Dh. In the most preferred embodiment, the metal carboxylate salt is aluminum stearate having a melting point ranging from about 135 kD to about 165 kD.

In another preferred embodiment, the melting point of the metal carboxylate is higher than the polymerization temperature in the reactor.

Other metal carboxylate salts include titanium stearate, tin stearate, calcium stearate, zinc stearate, boron stearate, and strontium stearate.

In one embodiment, the metal carboxylate salt may be combined with antielectrostatic agents such as fatty amines, for example adding zinc ketamine 990/2 AS, which is a combination of ethoxylated stearylamine and zinc stearate, or zinc ketamine 999/3 AS, which is ethoxylated stearylamine and zinc stearate. and octadecyl-3,5-di-th-butyl-4-hydroxyhydrocinnamate. Both of these combinations are available from Whitco Corporation, Memphis, Tennessee.

How to prepare the catalyst composition

The method of making a catalytic composition generally includes incorporating, contacting, synthesizing and/or blending a catalytic system or polymerization catalyst with a metal carboxylate salt.

In one embodiment of the method according to the invention, a conventional-type transition metal catalyst and/or a metallocene-type catalyst containing a bulk ligand is combined, contacted, combined and/or blended with at least one metal carboxylate salt. In the most preferred embodiment, the transition metal catalyst is a conventional type and/or a metallocene type catalyst containing a bulk ligand carried on a carrier.

In another embodiment, the steps of the method of this invention include forming a polymerization catalyst, preferably forming a portable polymerization catalyst, and contacting the polymerization catalyst with at least one metal carboxylate salt. In a preferred method, the polymerization catalyst includes a catalyst compound and an activator or a co-catalyst and a carrier, preferably a portable metallocene catalyst containing a bulk ligand.

Those familiar with the technology will realize that certain conditions of temperature and pressure must be applied to avoid, for example, loss of the effectiveness of the catalytic system, depending on the catalytic system and the metal carboxylate salt.

In one embodiment of the method of the invention, the metal carboxylate salt is in contact with the catalytic system,

A portable catalytic system is preferred, and the most preferable is a portable metallocene-type catalytic system containing a bulky ligand at ambient temperatures and pressures. It is preferable that the contact temperature used to combine the polymerization catalyst and the metal carboxylate salt range from 0°C to about 100°C, preferably from 15°C to about 75°C, and most preferably at about the temperature and pressure of the ambient atmosphere.

In a preferred embodiment, the polymerization catalyst and the metal carboxylate salt are brought into contact in an inert gaseous medium such as nitrogen. However, it is recognized that the combinatorial mixing of the polymerization catalyst and the metal carboxylate salt can be performed in the presence of one or more olefins, solvents, hydrogen, and the like.

In one embodiment, the metal carboxylate salt may be added at any stage during the preparation of the polymerization catalyst.

In one embodiment of the method of the invention, the polymerization catalyst and a metal carboxylate salt are combined in the presence of a liquid that may, for example, be mineral oil, toluene, hexane, isobutane, or a combination thereof. In a more preferable method, the metal carboxylate salt is combined with a polymerization catalyst that has been formed in a liquid, preferably in a slurry, or it is combined with a dried or substantially dry polymerization catalyst that has been formed in a liquid and slurry.

In an embodiment, the contact time between the metal carboxylate salt and the polymerization catalyst may vary depending on one or more conditions, temperature, pressure, type of mixing device, amounts of components to be combined, as well as the mechanism of adding the combination of polymerization catalyst and metal carboxylate salt to the reactor.

The polymerization catalyst, preferably a metallocene-type catalytic compound containing a bulk ligand and a carrier, should preferably be in contact with a metal carboxylate salt for a period of time ranging from about one second to about 24 hours, preferably from about 1 minute to about 12 hours, and preferably about 10 minutes. To about 10 hours and most preferably from about 30 minutes to about 8 hours.

In one embodiment, the weight ratio of the metal carboxylate salt to the weight of the transition metal of the catalytic compound ranges from about 0.01 to about 1,000, preferably from 1 to about 100, preferably from about 2 to about 50, and most preferably from 4 to about 20. In one embodiment, the weight ratio of the salt Metal carboxylate to transition metal weight of the catalyst compound from about 2 to about 20, preferably from about 2 to about 12, and preferably from 4 to about 10.

In another embodiment of the method of the invention, the weight percentage of the metal carboxylate salt based on the total weight of the polymerization catalyst ranges from about 0.5% by weight to about 500%

By weight, preferably from 1% by weight to about 25% by weight, preferably from about 2% by weight to about 12% by weight, and most preferably from about 2% by weight to about 10% by weight. In another embodiment, the weight percentage of the metal carboxylate salt ranges on a weight basis

The total amount of polymerization catalyst ranges from 1 to about 50% by weight, preferably from 2% by weight to about 30% by weight, and most preferably from about 2% by weight to about 20% by weight.

In one embodiment, when the process of this invention produces a polymeric product having a density greater than 0.91 g/cm3, the total weight percentage of the metal carboxylate salt based on the total weight of the polymerization catalyst is greater than 1 wt%. In yet another embodiment, when the process produces a polymeric product having a transfer density of more than 0.091 g/cm3, the total weight percentage of the metal carboxylate salt based on the total weight of the polymerization catalyst is greater than 3% by weight. If the polymerization catalyst includes a carrier, the weight of the carrier is included in the total weight of the polymerization catalyst.

It is believed that the higher the metal content of the activator, for example the aluminum content or the total aluminum content (alkyl aluminum content of the alamoxane compound), present in the polymerization catalyst, the greater the amount of metal carboxylate salt is required. Manipulating the amounts or loadings of the polymerization catalyst components, i.e. aluminum alloy, provides a means of controlling the level of the metal carboxylate salt.

The mixing techniques and equipment that may be used in the method of the invention are well known.

Mixing techniques may include any means of mechanical mixing, for example shaking, stirring, barrel stirring and rolling. Other techniques include the use of fluidization, for example in a fluidized bed reactor vessel where mixing is achieved by circulating gases. Examples of mixing equipment used to combine, according to the most preferred embodiment, a solid polymerization catalyst and a solid metal carboxylate salt include, but are not limited to, a ribbon mixer, an electrostatic mixer, a double cone mixer, a cylindrical stirring mechanism, a cylindrical roller, a dewatering device, a fluidized bed, a screw mixer, and a conical screw mixer.

In an embodiment of the method of the invention, a conventional portable type transition metal catalyst, preferably a portable metallocene type catalyst containing a bulky ligand, is stirred with a carboxylate salt

A metal for a period of time sufficient to thoroughly mix and/or come into contact with a significant portion of the carried catalyst with the metal carboxylate salt.

In a preferred embodiment of the invention, a catalytic system according to the invention is carried on a carrier material and the portable catalytic system is preferably substantially dried and/or preformed and/or substantially dry and/or smooth-flowing. In a particularly preferred method according to the invention, the preformed mobile catalytic system is contacted with at least one metal carboxylate salt. The metal carboxylate salt is dissolved in solution or in a slurry or is in a dry state. It is preferable for the metal carboxylate salt to be substantially dry or in a dried state. In the most preferable embodiment, the metal carboxylate salt is in contact with a portable catalytic system, preferably a portable catalytic system of the metallocene type containing a bulk ligand, in a rotating mixer under a nitrogen atmosphere, preferably a stirrer mixer, or in a fluidized bed mixing process, The polymerization catalyst and the metal carboxylate salt are in a solid state, i.e. they are both in a dry or substantially dehydrated state.

In an embodiment of the method of the invention, a conventional type transition metal catalyst compound, preferably a metallocene-type catalyst compound containing a bulky ligand, is in contact with a carrier to form a portable catalytic compound. In this method, an activator or cocatalyst of the catalytic compound is in contact with a separate carrier to form a portable activator or cocatalyst. It is understood that in this particular embodiment of the invention, the metal carboxylate salt is subsequently blended with the portable catalyst compound, mobile activator or portable co-catalyst, in any particular arrangement or mixed separately or mixed simultaneously or mixed with only one of the portable catalysts or preferably with the portable activator Before mixing it with the catalyst and activator or co-catalyst carried separately.

As a result of using a combination of a polymerization catalyst and a metal carboxylate salt according to the invention,

The overall flow of catalyst to the reactor should be optimized. Despite the fact that the flow of said catalyst is not as good as the catalyst without the metal carboxylate salt, the flowability of the catalyst and carboxylate combination according to the invention is no longer an issue. If it is necessary to improve the catalytic flow, define the technique

Use a box shaker, catalytic feeder brushes, feeder pressure relief tubes, and the like.

In another embodiment, both the polymerization catalyst and the metal carboxylate salt may come into contact with a liquid,

Such as mineral oil, and the resulting product is added to the polymerization process in a slurry state. In this particular embodiment, the polymerization catalyst is preferably portable.

In some polymerization processes, it is preferable to use carriers with smaller particle sizes. However, the operability of these processes is difficult. It has been discovered that when a combination of a polymerization catalyst and a metal carboxylate salt according to the invention is used, smaller particle size support materials may be used successfully. For example, silica with an average particle size ranging from about 10 microns to 80 microns can be used. Silica materials of this size are available from Crossfield Limited, Warrington, England, eg Crossfield ES-70 with an average particle size of 35 to 40 microns. Without wanting to be bound by any particular theory, it is usually believed that the use of support materials with a smaller average particle size produces finer particles and results in the portable catalyst being subjected to additional plating. It is also believed that the use of metal carboxylates with a polymerization catalyst ensures better particle growth during polymerization. This good particle morphology is believed to result in fewer particles forming and a lower susceptibility to delamination. Thus, the use of metal carboxylate allows the use of a support material with a smaller particle size.

In an embodiment, the method of this invention provides for the joint injection of an unloaded polymerization catalyst and a metal carboxylate salt into the reactor. In one embodiment, the polymerization catalyst is used in a non-containing form, preferably in a liquid form as described in detail in US Patents 5,317,036 and 5,693,727 and European Patent 593,083 A-0, all of which are incorporated into this statement by reference . The polymerization catalyst in liquid form with a metal carboxylate salt may be fed to a reactor using the injection methods described in the International Patent Publication in accordance with PCT No. 97/46599, which is fully incorporated into this Statement by reference.

When using a combination of a metal carboxylate salt and a portable metallocene catalytic system containing a bulky ligand, the molar ratio of the activation component metal to the metallocene catalyst complex containing a bulky ligand ranges from 1:0.3 to 10,000:1, preferably from 100:1 to 1:5000 and most preferably from 1:500 to 1:2000.

Polymerization process

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, a gas phase, a slurry phase, under high pressure, or a combination thereof. A particularly preferred process is the polymerization in a gas phase or slurry phase of one or more olefins, at least one of which is ethylene or propylene.

In one embodiment, the process of this invention is directed toward a solution or phase polymerization process

A reflux or gas phase of one or more olefinic monomers containing from 2 to 30 carbon atoms

Preferably from 2 to 12 carbon atoms, and preferably from 2 to 8 carbon atoms. This invention is particularly well suited to the polymerization of two or more monomers of olefins including ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and 1-hexene 1-actin.

And 1-decene.

Other monomers useful in the invention process include ethylene unsaturated monomers, binary olefins containing from 4 to 18 carbon atoms, exchangeable or non-exchangeable dienes, polydimers, vinyl monomers, and cyclic olefins. Examples of useful monomers in this invention include, but are not limited to, norbornene, norbornadiene, isobutylene, phenylbenzobutane, styrene compounds, alkyl-substituted styrene, ethylidene norbornene, isoprene, dicyclopentadiene and cyclopentene.

In a more preferred embodiment of the process of the invention, a copolymer is produced from ethylene, wherein the copolymer is polymerized containing at least one alpha-olefin having from 4 to 15 carbon atoms

Preferably 4 to 12 carbon atoms and most preferably 4 to 8 carbon atoms, with ethylene in a gas-phase process.

In another embodiment of the process of the invention, ethylene or propylene is polymerized with at least two different comonomers, one of which may be a diene, to form a terpolymer.

In one embodiment, the invention directs to a process, particularly a gas-phase or reflux-phase process, for the polymerization of propylene alone or with one or more monomers including ethylene, and olefins containing from 4 to 12 carbon atoms. Polypropylene polymers may be produced using bridge catalysts, particularly of the metallocene type, containing a bulky ligand as described in U.S. Pat. Nos. 5,296,434 and 5,278,264, which are incorporated herein by reference.

To them for reference.

Typically, a continuous cycle gas-phase polymerization process is used where in one part of the cycle of a reactor system, a circulating gas stream, also called a recirculating stream or dilution medium in the reactor, is heated by the heat generated by 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. Generally, a gas stream containing one or more monomers in a gaseous fluidized bed process used to produce polymers is circulated continuously through a fluidized bed in the presence of a catalyst exposed to reactive conditions. The gaseous stream is drawn from the fluidized bed and recycled to the reactor. At the same time, the polymer product is withdrawn from the reactor and a new monomer is added to replace the polymerized monomer (see, for example, US Patents Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, and 5. 352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, all of which are fully incorporated herein by reference. for reference).

Reactor pressure in the gas-phase process may vary from about 100 psi (690 kPa) to about 500 psi (3448 kPa), preferably in the range from about 200 psi (1379 kPa) to about 400

psi (2759 kPa) and best in the range from about 250 psi (1724 kPa) to about 350 psi (2414 kPa).

The reactor temperature in the gas-phase process may vary from about 30°C to about 120°C, preferably from 60°C to about 115°C, preferably from about 70°C to 110°C, and most preferably from about 70°C. M to about 95 Dh.

Other gas-phase processes according to the process of this invention include those described in U.S. Patents 5,627,242, 5,665,818, and 5,677,375 and European Patent Application Publications Nos. A-0 794 00, A-0 802 202, and A2 0 891 990. 421 634 -B, all of which are fully incorporated herein by reference.

In a preferred embodiment, the reactor used in this invention can, by means of the process of this invention, produce from over 500 pounds of polymer per hour (227 kg/hour) to about 200,000 pounds/hour (90,900 kg/hour) or more, preferably more than 1,000 pounds. /hour (455 kg/hour), better than 10,000 lb/hour (4,540 kg/hour), better than 2,500 lb/hour (11,300 kg/hour), better than 35,000 lb/hour (15,900 kg/hour). ) Better yet, more than 50,000 lb/h (22,700 kg/h) and more preferably, more than 65,000 lb/h (29,000 kg/hour) to more than 100,000 lb/hour (45,500 kg/hour).

The polymerization process in the slurry phase generally uses pressures in the range from about 1 to about 50 atmospheres and even higher and temperatures in the range from 0°C to about 120°C. In the slurry phase process, a suspension of solid particulate polymer is formed in a liquid polymerization buffer to which ethylene, comonomers, and hydrogen are added, often along with the catalyst. The suspension containing the diluent is removed from the reactor intermittently or continuously, where the volatile components are separated from the polymer and recycled, possibly after distillation into the reactor. The liquid diluent used in the polymerization medium is usually an alkane containing from 3 to 7 carbon atoms. The medium used should be liquid under polymerization conditions and relatively inert. And when

If a propane medium is used, the process should be operated at a temperature and pressure higher than the critical value of the reaction buffer. It is preferable to use a medium of hexane or isobutane.

The preferred polymerization technique according to the invention is called particle polymerization or slurry process, where the temperature is maintained at a value lower than the temperature at which the polymer turns into a solution. This technique is well known in the art and is described for example in US Patent 3,248,179, which is fully incorporated into this statement by reference. Other slurry processes include those that use a loop reactor and those that use a group of stirred reactors in series or parallel, or combinations thereof. Examples of slurry processes include, but are not limited to, continuous loop or stirred tank processes. Other examples of rediging operations are also described in US Patent 4,613,484, which is fully incorporated into this statement for reference.

In an embodiment, the reactor used in the slurry process according to the invention can, by means of the process of this invention, produce more than 2,000 pounds of polymer per hour (907 kg/hour), more preferably more than 5,000 pounds per hour (2,268 kg/hour), and more preferably more than 10,000. lbs/hour (4540 kg/hour). In another embodiment, the slurry reactor in the process of the invention produces more than 15,000 pounds of polymer per hour (6,804 kg/hour) and preferably more than 25,000 pounds/hour (11,340 kg/hour) to about 100,000 pounds/hour (45,500 kg/hour). .

Examples of solution processes are described in US Patent Nos. 4,271,060, 5,001,205, 5,236,998, and 5,589,555, which are fully incorporated herein by reference.

The preferred process of the invention is a process preferably in the slurry or gas phase operating in the presence of a metallocene catalytic system containing a bulk ligand and in the absence or essentially no scavengers such as triethyl aluminum chloride, trimethylaluminium and tert-isobutyl aluminum. And tert-p-hexyl aluminum, diethyl aluminum and dibutyl

Zinc and the like. This preferred process is described in the International Patent Bulletin in accordance with PCT No. 96/08520 and US Patent Nos. 5,712,352 and 5,763,543, which are incorporated herein by reference. However, it has been discovered that a polymerization process employing a combination of the catalyst system and a metal carboxylate salt according to the invention may be operated using a small amount of scavenger with reduced or no effect on process operability and catalyst performance. Thus, this invention provides in one embodiment a process for polymerizing one or more olefins in a reactor having a metallocene-type catalytic system containing a bulk ligand, a metal carboxylate salt, and a scavenger.

In an embodiment, the yield of the polymerization catalyst and/or catalyst composition representing the polymerization catalyst and the metal carboxylate salt exceeds 1,500 g of polymer per gram of catalyst, preferably more than 200 g of polymer per gram of catalyst, preferably more than 2,500 g of polymer per gram It is preferable to exceed 3000 g of polymer per g of catalyst.

In another embodiment, the yield of the polymerization catalyst and/or the catalyst composition representing the polymerization catalyst and the metal carboxylate salt exceeds 2,000 g of polymer per gram of catalyst, preferably exceeding 3,000 g of polymer per gram of catalyst, preferably exceeding 4,000 g of polymer per g of catalyst, preferably more than 5000 g of polymer per g of catalyst.

In one embodiment, the polymerization catalyst and/or catalyst composition has a reactivity ratio typically less than 2 and more commonly less than 1. The reactivity ratio is defined as the molar ratio of the copolymer 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 copolymer to the monomer present in the polymeric product to be produced. In a preferred embodiment, the reactivity ratio is less than 0.6, preferably less than 0.4, and more preferably less than 0.3. In the most preferred embodiment, the monomer is ethylene and the comonomer is olefin containing 3 or more carbon atoms

The best alpha-olefin contains 4 or more carbon atoms, and the most preferred alpha-olefin is chosen from the class consisting of 1-butene, 4-as-1-pentene, 1-pentene, 1-hexene, and 1-actin.

In another embodiment of the invention, when transferring from a first polymerization catalyst to a second polymerization catalyst,

It is preferable that where the first and second polymerization catalysts are a metallocene-type catalytic compound containing a bulky ligand, and preferably where the second polymerization catalyst is a metallocene-type bridge catalytic compound containing a bulky ligand, it is preferable during the transition to use a catalyst composition of an incorporated metal carboxylate salt. With a metallocene bridge catalyst containing a bulky ligand.

When the polymerization process begins, especially the gas phase process, there is a high possibility of workability problems. Thus, in this invention it is desirable to use a combination of a polymerization catalyst and a metal carboxylate salt at startup to reduce or eliminate startup problems. In addition, it is also recognized that once the reactor is running at steady state, a transition step to the same or a different polymerization catalyst can be performed without the presence of the metal carboxylate salt.

In another embodiment, during an inactivated or about to be inactivated polymerization process, a combination of a polymerization catalyst and a metal carboxylate salt according to the invention should be switched to. This transition between polymerization catalysts is thought to occur when workability problems increase. Signs of interoperability problems with the technology have been identified. Some of these signs in a gas phase process include temperature deviations in the reactor, sudden pressure changes, excessive static generation, unusually high static sparks, formation of thick pieces, delamination, and the like. In one embodiment, the metal carboxylate salt may be added directly to the reactor especially when workability problems increase.

It has also been discovered that using a polymerization catalyst combined with a metal carboxylate salt according to the invention facilitates the production of high density polymers with a fractional melt index. In one embodiment, the invention provides a process for polymerizing one or more olefins in a reactor in the presence of a polymerization catalyst compatible with

A metal carboxylate salt to produce a polymeric product with a melting index of less than about 1 dg/min and a density of more than 0.92 g/cm3. The best is a polymeric product with a melting index of less than about 0.75 dg/min and a density of more than 0.925 g/cm3. It is preferable that the polymerization catalyst used be a metallocene-type catalyst that contains a bulky ligand. It is preferable that the process be a gas phase process and that the polymerization catalyst includes a carrier material.

It should be recognized that by using a combination of a polymerization catalyst and a metal carboxylate salt according to the invention, the transition to one of the more difficult polymer classes to produce will be easier. Thus, in one embodiment, the invention directs to a process for polymerizing one or more olefins in the presence of a first catalytic composition under stable conditions and preferably under gas phase process conditions, to produce a first polymeric product. The first polymeric product will have a density of more than 0.87 g/cm3, a melting index of more than 0.9 g/cm3, preferably more than 0.91 g/cm3, and a melting index in the range from 1 decigram/minute to about 200 decigrams/minute, preferably more than 1 decigram/minute. To about 100 decigrams/minute, and it is preferable to exceed 1 decigrams/minute to about 50 decigrams/minute, and it is most preferable to exceed 1 decigrams/minute to about 20 decigrams/minute. This process also includes the step of transitioning to the synthesis of a second catalyst to produce a second polymeric product having a density of more than 0.92 g/cm3, preferably greater than 0.925 g/cm3, and a magma index of less than 1 decigram per minute, preferably less than 0.75 decigram per minute. The second catalyst composition comprises a conventional type transition metal catalyst and/or a metallocene type catalyst containing a bulk ligand and a metal carboxylate salt. Also within the scope of this particular embodiment is the transition from a first polymeric product having an I2/I21 value (as described below) of less than 25 to a second polymeric product having an I2/I21 value of greater than 25, preferably greater than 30, and preferably greater than 35. .

In yet another embodiment, the process of this invention includes alternating between the use of a first catalyst composition comprising a mixture of a first polymerization catalyst and a metal carboxylate salt and a catalyst composition of a second polymerization catalyst devoid of the metal carboxylate salt to improve the overall operability of the process. And in embodiment

Else, the first and second catalyst compositions described above may be used simultaneously for example as a mixture or injected into the reactor separately. In any of these embodiments, the first and second polymerization catalysts are either 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. Polymers resulting from the process of this invention include linear low-density polyethylene, elastomeric polymers, elastomeric polymers, high-density polyethylenes, low-density polyethylenes, polypropylene, and polypropylene copolymers.

Polymers, typically ethylene-based polymers, have densities in the range of 0.68.

g/cm3 to 0.97 g/cm3, preferably in the range from 0.88 g/cm3 to 0.965 g/cm3

It is better in the range from 0.900 g/cm3 to 0.96 g/cm3, and even better in the range from 0.905 g/cm3 to 0.95 g/cm3, and even better in the range from 0.910 g/cm3 to 0.94 g/cm3, and it is most preferable to increase More than 0.915 g/cm3, preferably more than 0.92 g/cm3, and absolutely preferable to exceed 0.925 g/cm3.

The polymers produced by the process of this invention usually have a molecular weight distribution and a ratio of weight average molecular weight to numerical average molecular weight (Mn/Mw) in excess of 1.5 to about 15, and in particular ranging from above 2 to about 10, preferably ranging from more than about 2.2. To less than about 8 and most preferably from 2.5 to 8. The Mn/Mw ratio can be measured by gel depletion chromatography techniques, which are well known in technology.

Also, the polymers of this invention typically have a narrow compositional distribution as measured by the compositional distribution breadth index (CDBI). Further details of determining the CDBI value for a particular copolymer are known by those familiar with the technique. Consider, for example, the patent bulletin

International pursuant to Patent Cooperation Treaty No. 93/03093 of 18 February 1993 which is fully incorporated into this Statement by reference.

In an embodiment, metallocene-type catalytic polymers containing a bulky ligand according to the invention have CDBI values typically ranging from more than 50% to 99%, preferably from 55% to 85%, and more preferably, from 60% to 80%, and more preferably, from more than 60%, and more preferably. More than 65%.

In another embodiment, the polymers generated by a conventional type transition metal catalyst have a CDBI value of less than 50%, more preferably less than 40%, and more preferably less than 30%.

In an embodiment, the polymers according to this invention have an melt index (MI) or (I2) as measured by ASTM D-1238-E in the range from 0.01 dg/min to 1000 dg/min and better from about 0.01 dg/min to about 100 dg/min, preferably from about 0.1 pg/min to about 50 dg/min and most preferably from about 0.1 dg/min to about 10 dg/min.

The polymers of the invention in one preferred embodiment have a melt index ratio of (I2/I21)

(Where I21 is measured according to ASTM-D1238-F) ranging from

10 to less than 20, and preferably from about 15 to less than 25.

The polymers of the invention in one preferred embodiment have a melt index ratio of (I2/I21)

(Where I21 is measured according to ASTM-D-1238-F) more than 25

It is better for it to be more than 30, and it is better for it to be more than 40, and it is better for it to be more than

50 It is most preferable that it be more than 65.

In yet another embodiment, propylene-based polymers are produced in the process of this invention.

These polymers include asymmetric polypropylene, homopolypropylene, and rotational polypropylene. Other propylene polymers include shock, block, or random copolymers of propylene.

The polymers produced by the process of the invention are useful in molding processes such as film, sheet, or fiber extrusion, co-extrusion, blow molding, injection molding, and rotary molding. Films include blow molded, co-extruded or laminating films useful as shrink films, suspension films, stretch films, sealing films, oriented films, snack wrappers, rigid bags, grocery bags, baked and frozen food wrappers, medical drug wrappers, industrial liners and films. .. Etc. in food contact and non-food contact uses. Fiber manufacturing includes magma swirling, solution swirling, and magma blowing to be used in woven or non-woven form to make filters or fabrics for baby diapers, medical gowns, geotextiles, etc. Extruded materials include medical tubing, wire and cable coatings, geomembranes and pond liners, and molded materials include single and multi-layer assemblies in the form of bottles, tanks or materials. These include wide-bore items, rigid food bowls, toys, etc.

Examples

The following examples are provided to understand this invention more fully, including its representative advantages

The polymer properties were determined through the following test methods: Density was measured according to the American Society for Testing Materials ASTM-D-1238 method.

The denaturation factor in the tables below shows the workability of the catalyst. The higher the value, the greater the amount of observed dirt. A soiling factor of zero indicates that there is no significant staining or no visible staining. A smear factor of 1 indicates light smear, where a slight layer of polymer is deposited on the stirrer blades in a polymerization reactor containing a 2-litre isobutane slurry and/or no lamination on the reactor body. A fouling factor of 2 indicates more than light fouling, where a heavy, semi-greasy layer of polymer is deposited on the stirrer blades and/or the reactor body wall has little delamination with a band width of 1 to 2 inches (2.54 to 5.08 cm) on the wall of the reactor. Reactor. A denaturation factor of 3 indicates moderate denaturation, as a thicker, latex-like polymer layer is deposited on the surface.

Stirrer blades and some soft blocks in the reactor and/or minimal lamination on the reactor body with a band width of 2 to 3 inches (5.08 to 7.62 cm) on the reactor wall. A denaturation factor of 4 indicates more than moderate denaturation, whereby a thick, latex-like polymeric layer and/or some solid polymer blocks or balls and/or lamination are deposited on the wall of the reactor structure with a band width of 3 to 4 inches (7.62 to 10.2 cm).

The effectiveness shown in the tables below is measured by the number of grams of polyethylene (pe) per gram of polymerization catalyst per hour (g PE/g of catalyst. hour)

Comparison example (1)

Catalyst preparation (A)

Use dimethylsilyl-di(tetrahydroadenyl)zirconium dichloride (Me2Si(H4Ind)2ZrCl2), supplied by Albemarle Corporation of Baton Rouge, Louisiana.

As the metallocene-type bridge catalyst containing a bulky ligand used in the comparison example (1). Where the catalyst compound Me2Si(H4Ind)2ZrCl2) was loaded onto silica of the

Crossfield 70-ES dewatered at 600 dm contains approximately 1% by weight of water lost on ignition (LOI) and the LOI value is measured by determining the weight lost from the carrier heated and held at about 0100 dm for about 22 hours. Crossfield 70-ES silica has an average particle size of 40 microns and is available from Crossfield Limited in Warrington, England.

The first step in making the bulky ligand-containing mobile metallocene-type catalyst described above involves formation of a precursor converter. Add 460 lb (209 kg) of wet and dried toluene to a stirred reactor and then add 1060 lb (482 kg) of 30% by weight methylalmoxane (MAO) in toluene (available from Albemarle Company in Baton Rouge, Louisiana). Add 947 pounds (430 kg) of a 2% by weight solution of dimethylsilyl-di(tetrahydroindenyl)zirconium dichloride and 600 pounds (272 kg) of

Additional toluene to the reactor. The precursor solution is then stirred at a temperature ranging from 80°F (degrees Fahrenheit) to 100°F (i.e., 26.7°C to 37.8°C) for one hour.

While stirring the above-prepared precursor solution, 850 pounds (386 kg) of a dehydrated silica carrier at 600 D.C. of the Crossfield type is slowly added to the precursor solution and the mixture is stirred for 30 minutes at a temperature ranging from 80 D.F. to 100. Dhs. (from Dhs. 26.7 to Dhs. 37.8). After 30 minutes, add 240 pounds (109 kg) of a 10% by weight toluene solution containing (N,N-di(2-hydroxyethyl)octadecylamine (2(C18H37N(CH2CH2OH))) type 990-AS available. As Kemamine 990-AS from Whitco Corporation, Memphis, Tennessee, with an additional 110 lb (50 kg) of toluene wash and then mix the contents of the reactor for 30 minutes while heating to 175 dF (79 dF). 30 minutes, vacuum and dry the polymerization catalyst mixture at 175 kF (79 kW) for about 15 hours until a smooth flowing powder is obtained. The weight of the final polymerization catalyst was 120 lb (544 kg), the percentage of Zr by weight was 0.35 and the percentage of Al by weight was 12. Example (1)

Catalyst preparation (B)

A 1 kg sample of the polymerization catalyst prepared as described in comparison example (1), i.e. catalyst (A), was weighed and placed in a 3-liter glass bottle under an inert atmosphere. Dry 40 g of Aluminum Stearate No. 22 (Aist No. 22), i.e. CH3(CH2(16COO)2A1-OH)

Supplied by Whitco Corporation, Memphis, Tennessee, dried in vacuum at 85°C, added to the vial, stirred, and mixed for 20 minutes at room temperature. It appeared that aluminum stearate was dispersed homogeneously throughout the catalyst particles.

Example (2)

Catalyst preparation (c)

A 1 kg sample of the polymerization catalyst prepared according to what was described in the comparison example (1) was weighed.

That is, the catalyst (1) was placed in a 3-liter glass bottle in an inert atmosphere. And dry 20 g of Whitco Aluminum Stearate No. 22 (Alst No. 22) i.e. CH3(CH2)16COO)2 A1-OH) provided by

Whitco Corporation, Memphis, Tennessee, dried in vacuum at 85°C, added to the vial, stirred, and mixed for 20 minutes at room temperature. Aluminum stearate appeared to be dispersed homogeneously throughout the catalyst particles.

Example (3)

Catalyst preparation (d)

A 1 kg sample of the polymerization catalyst prepared according to what was described in the comparison example (1), i.e. the catalyst (1), was weighed and placed in a 3-liter glass bottle under an inert atmosphere. Dry 10 g of Whitco Aluminum Stearate No. 22 (AlSt No. 22), i.e. CH3(CH2(16COO)2 AL-OH), supplied by Whitco Corporation, Memphis, Tennessee.

Dry in vacuum at 85°C, add to the flask, stir the contents and mix for 20 minutes at room temperature. Aluminum stearate appeared to be dispersed homogeneously throughout the catalyst particles.

Polymerization process using catalysts A to D

A two-liter autoclave reactor was fed in the presence of a nitrogen detergent stream with 0.16 mmol of triethyl aluminum (teal), then with 20 cm3 of the comonomer 1-hexene and 800 cm3 of diluted isobutane. The contents of the reactor were heated to 80 d.m., after which 100 mg of each of the portable polymerization catalysts prepared above, i.e., catalysts (A), (B), (C, and (D),) were polymerized separately and using the following method: Each polymerization catalyst was added separately. Synchronized with ethylene to the reactor to obtain a total reactor pressure of 325 psi (2240 kPa). The reactor temperature was maintained at 85°C and the polymerization was left to continue for 40 minutes. After 40 minutes, the reactor was cooled, the ethylene was drained, the polymer was dried and weighed to obtain the polymeric yield. Table (1) below provides the resulting effectiveness data in addition to its characteristics

Solidification observed using catalyst (A), which is devoid of aluminum stearate, and catalysts (B) to (D), which contain different levels of aluminum stearate.

<img file="SA938B1_D0003.tif" />

Table (1) shows the effect of different levels of aluminum stearate on catalyst effectiveness and workability.

Comparison example (2)

Catalyst preparation (e)

First feed 2 liters of toluene, then 1060 g of 30% methylalmoxane solution.

by weight in toluene (available from Albemarle Co., Baton Rouge, Louisiana) and then 23.1 g of di(3,-dimethyl-p-butylpentadienylcyclo)zirconium dichloride in solution

Dilute 10% in toluene into a 2-gallon (7.57 L) reactor. The mixture was stirred for 60 minutes at room temperature, then 850 g of silica (Davison 948, dehydrated at 600 dm, available from W.R. Grace Company, Davison Chemical Development, Baltimore, Maryland) was added to the liquid while stirring. slowly. The stirring speed was increased for about ten minutes to ensure the dispersion of silica in the liquid, and then an appropriate amount of toluene was added to form a slurry whose state ranges from liquid to solid and has a consistency of 4 cm3/g. Mixing was continued for 15 minutes at 120 rpm, after which 6 g of Kemamine 990-AS (supplied by Whitco Corporation, Memphis, Tennessee) was dissolved in 100 cm of toluene, then the mixture was added and stirred for 15 minutes. Then drying was carried out under vacuum and in the presence of a detergent stream

Nitrogen at 175 dF (79.4 dF). When the polymerization catalyst containing the silica carrier appeared to be smooth-flowing, it was cooled to a lower temperature and emptied into a nitrogen-cleaned vessel. Approximately 1 kg of dry polymerization catalyst was obtained due to some attributable losses

To drying.

Example (4)

Catalyst preparation (f)

A sample of the polymerization catalyst prepared according to what was described in comparison example (2), i.e. the catalyst (e), was synthesized in dry form with an amount equal to 2% by weight of Whitco Aluminum Stearate.

22 (Alst No. 22) (supplied by Whitco Corporation, Memphis, Tennessee) based on

Total weight of portable polymerization catalyst. AlSt No. 22 was dried in a vacuum oven for 12 hours at 85°C, then the polymerization catalyst was dried in the presence of nitrogen using AlSt No. 22. Table (2) shows the benefits of adding the metal carboxylate salt in these examples, i.e. aluminum stearate, to the polymerization catalyst. . These examples also show that the metal carboxylate salt has almost no effect on the molecular weight properties of the polymer formed.

The table below shows the results of the polymerization experiments for catalysts (e) and (f) using the same process as previously described above for catalysts (a) to (d).

<img file="SA938B1_D0004.tif" />

Comparison example (2)

Catalyst preparation (g)

Feed 1060 g of a 30 wt% methylalmoxane (MAO) activated solution in toluene (PMAO, a modified MAO available from AkzoNobel, LaPorte, Texas), then 1.5 L of toluene to a 2-gallon (7.57 L) reactor. . While stirring, 17.3 g of zirconium di(3,1-methyl-p-butylpentadienylcyclo)zirconium dichloride were added,

It is a metallocene catalytic compound containing a bulk ligand in the form of an 8% solution by weight in toluene to the reactor and the mixture is stirred for 60 minutes at room temperature to form the catalyst solution. The contents of the reactor were emptied into a flask and 850 g of dehydrated silica at 600 dM (available from Crossfield Limited, Warrington, England) was fed to the reactor. The catalyst solution in the flask was then slowly added to the silica carrier in the reactor while stirring slowly. An additional amount equal to 0.35 cm3 of toluene was added to ensure the desired consistency of the slurry was obtained and the mixture was stirred for an additional 20 minutes. 6 g of chemamine 990-AS (available from Whitco Corporation, Memphis, TN) was added as a 10% solution in toluene and stirred for 30 minutes at room temperature. Then the temperature was raised to 68°C (155°F) and a vacuum was applied to dry the polymerization catalyst. Drying continued for about 6 hours with slow stirring until the polymerization catalyst appeared

Smooth flow. It was then emptied into a vial and stored in a nitrogen atmosphere. He got 1006

g due to some loss in the drying process. Analysis of the polymerization catalyst showed that the percentage of zirconium = 0.3% by weight and the percentage of aluminum = 11.8% by weight

Examples (5) and (6)

In Examples (5) and (6), the polymerization catalyst prepared as described in Comparison Example (3), i.e., catalyst (G), is injected with 4% by weight and 8% by weight of Witco Aluminum Stearate No. 22 (Alst No. 22) (provided From Whitco Corporation, Memphis, Tennessee) on a consignment basis

The catalyst was injected into the polymerization reactor. The results of polymerization experiments using...

Catalysts (g), (h) and (i) are in the same process as previously described for catalysts (a) to (Dr)

<img file="SA938B1_D0005.tif" />

Table 3 shows that with the use of a more effective catalyst that is subject to more contamination, the formation of aluminum stearate is effective. It also clarifies that aluminum stearate does not fundamentally change the properties of the product.

Examples (7) to (11)

Examples (7) and (8) use the same catalyst described in comparison example (3), i.e., catalyst (G) with calcium stearate (CaSt) (catalyst J) being used as the metal carboxylate salt in Example (7) and zinc stearate (ZnSt) ( Catalyst K) in example (8). Both CaSt and ZnSt are available from Mallinckrodt Corporation, Phillipsbury, New Jersey. The polymerization process used to test the two catalyst structures according to Examples (7) and (8) was identical to what was described and used above for catalysts (a) to (d).

Examples (9) and (11) use the same catalyst described in comparison example (1), i.e., catalyst (A) with the first aluminum stearate (Example (9), catalyst (L)) being used as a metal carboxylate salt and the second aluminum stearate (Example (Example (Example) 10), catalytic (m)), and aluminum tristearate (Example (11), catalytic (n)). The polymerization process will be described later in this statement and will be used in Examples (12) to (15), to test the catalyst structures according to Examples (9) to (11), i.e., catalysts (L), (M), and (N). Table (4) below presents these results.

<img file="SA938B1_D0006.tif" />

Examples (7) and (8) illustrate the use of different metal carboxylate salts. Specifically in Examples (7) and (8), it is shown that stearate metals, Ca and Zn, are effective in reducing dirt. Examples (9), (10) and (11) illustrate many types of aluminum carboxylate salts, especially those different active forms of aluminum. It is noted from the data in Table (4) that the first, second and third stearate compounds are the most effective.

Examples from (12) to (15)

It will be used in the dry synthesis method described in Example (1) with catalyst (A) for comparison example (1), with different types of metal carboxylate salts. Table (5) shows the quantity and type of metal carboxylate salt. The following polymerization process described below was used for each combination of polymerization catalyst and metal carboxylate salt, i.e. catalysts (S) and

(P), (Q) and (R).

Polymerization process for catalysts (12) to (15)

Feed 0.16 mmol of triethyl aluminum (TEAL), then 25 cc of 1-hexene comonomer and 800 cc of diluted isobutane to a 2-liter autoclave reactor in the presence of a detergent stream of nitrogen. The contents of the reactor were heated to 80 d.C. Then 100 mg of each mixture of portable polymerization catalysts and the metal carboxylate salt described above (catalyst (A) with specific amounts of the metal carboxylate salt as listed in Table (5)) was polymerized separately according to the method. The following: Each combination of the polymerization catalyst and the metal carboxylate salt was added simultaneously with ethylene to the reactor to obtain a total reactor pressure of 325 psi (2240 kPa). The reactor temperature was maintained at 85 D°C and the polymerization process was left to continue for 40 minutes. . And after. After 40 minutes, cool the reactor, drain the ethylene, dry the polymer and weigh to obtain a polymeric product.

The results are shown in Table (5) shown below. It is particularly important that these examples (12), (13), (14) and (15) show that the presence of a large group of R is preferable to metal carboxylate salts, specifically aluminum carboxylate salts.

<img file="SA938B1_D0007.tif" />

Examples (16) to (18) and comparison example (4):

Examples (16), (17), and (18) and the comparison example (4) illustrate the effectiveness of using a metal carboxylate salt, especially aluminum stearate, in a gas-phase process that uses a fluidized bed combined with a metallocene-type catalytic system containing a bulky ligand to produce types of polymer that are difficult to obtain. Usually produced especially with regard to workability. Items are usually difficult to produce

With a fractional magma index and higher density if the operability of the reactor is considered. The polymerization catalyst used in the polymerization processes was operated according to examples (16), (17) and (18) in a process that will be described below and the results are shown in Table (6) below.

Polymerization process

The catalysts (A), (B), and (F) described above were tested individually in a continuous gas-phase fluidized-bed reactor containing 60 nominal attached reactors 18 inches long and having an internal diameter of 16.5 inches. The fluidized bed consists of polymeric granules. The gaseous feed streams of ethylene, hydrogen, and liquid copolymer were mixed together in a T-mixing system and added down the reactor bed to the recirculating gas line. 1-hexene was used as the comonomer. Individual flow rates for ethylene, hydrogen, and copolymer were adjusted to maintain the desired structural properties. And adjust the ethylene concentration to maintain a constant partial pressure of ethylene. Adjust the hydrogen concentration to maintain a constant molar ratio of hydrogen to ethylene. The concentration of all gases was measured by continuous gas chromatography to ensure a relatively constant composition in the recycled gas stream. The solid metallocene portable catalytic system, which contains a bulky ligand shown in Table 6, was injected directly into the fluidized bed using purified nitrogen at a rate of 1.5 lb/hour (0.68 kg/hour). The reaction bed of growing polymer particles is maintained in a fluidized state by the continuous flow of supplementary feed and recirculating gas through the reaction bed. An apparent gas velocity of 1 to 3 ft/s (30.5 cm/s to 91.4 cm/s) was used to achieve this. The reactor was operated under a total pressure of 300 psi (2069 kPa), a reactor temperature of 85 C, and an apparent gas velocity of 2.25 ft/s to achieve the required fluidization of the granules. To maintain a constant reactor temperature, the temperature of the recycled gas was continuously adjusted to accommodate any changes in the rate of heat generation due to polymerization. The fluidized bed is maintained at a constant height by withdrawing part of the bed at a rate equal to the rate of formation of the particulate product. And transport the product properly

It is semi-continuous by using a series of valves to a constant volume chamber, which drains back to the reactor at the same time. This allows for highly efficient product removal while at the same time recycling a significant portion of the unreacted gases back to the reactor. The product is cleaned to remove escaping hydrocarbons and treated with a small stream of humidified nitrogen to immobilize any trace amounts of remaining catalyst.

<img file="SA938B1_D0008.tif" />

(1) Indicates one pound of polymer per pound of polymerization catalyst

By using metal carboxylate salts in combination with polymerization catalysts, reactor operability is dramatically improved. Table (6) shows a gas-phase reactor that operates without any problems in producing polymers with a fractional melt index for several layer transformations (BTO). Specifically, what is shown is that using a polymerization catalyst without a metal carboxylate salt, as described in comparison example (4) (without aluminum stearate), the reactor stopped due to soiling and delamination in less than 3 layer transitions at a magma index of about 1.5 dg/min and a density of 0.188. g/cm3. In an embodiment of the invention, the process runs for a period of time in excess of 4 class transitions, preferably more than 5 class transitions, and preferably more than 6 class transitions. A layer shift occurs when 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.

It has been known in technology that reducing the bulk density of the resin may improve the workability of a polymerization process, specifically a gas-phase polymerization process in a fluidized bed. It is noted from Table (6) that the bulk density of the resin did not change significantly, but the operability of the process according to the invention was amazing and substantially improved when a metal carboxylate salt was incorporated with the polymerization catalyst.

Although the present invention has been described and illustrated by reference to particular embodiments, those familiar with the art will recognize that the invention may include changes that may not necessarily be described herein. For example, it should be recognized that it is possible to add a metal carboxylate salt to the reactor in addition to bringing it into contact with the catalytic system according to the invention. It is also realized that the process according to the invention can be used in a chain reactor polymerization process.

For example, a portable metallocene bridge catalytic system containing a bulky ligand free of a metal carboxylate salt is used in one reactor, and a portable metallocene bridge catalyst system containing a bulky ligand that may come into contact with a metal carboxylate salt is used in another reactor or vice versa. It is also recognized that components of the metal carboxylate salt, i.e. the carboxylic acid and the metal compound, e.g. the metal hydroxy compound, may be added to the reactor or to the polymerization catalyst for formation at the reaction site or with the catalyst. It is also recognized that the metal carboxylate salt may be carried separately on a carrier different from the polymerization catalyst, preferably a portable polymerization catalyst. For this reason, reference should only be made to the appended claims for the purpose of determining the actual scope of this invention.