Catalytic composition and methods for preparation thereof as well as use thereof in polymerization process

FIELD: polymerization catalysts.

SUBSTANCE: invention provides catalytic composition prepared from polymerization catalytic system and at least one gelation agent, said gelation agent being selected from group including diester phosphates, steroid and anthryl derivatives, amino acid-type gelation agents, and tetraoctadecylammonium bromide and said polymerization catalytic system being selected from common-type catalytic compounds with transition metal and metallocene catalytic compounds. Invention discloses method of preparing indicated catalytic system and a method of continuous polymerization of an olefinic monomer.

EFFECT: expanded in catalytic polymerization processes.

17 cl, 2 tbl

 

The present invention relates to a catalytic composition, method for preparing this catalyst composition and to its use in the polymerization of olefins. The object of the invention, in particular, is a method for preparing a catalytic composition comprising or prepared from a polymerization catalyst and one gelatinizing agent or organizationsfor.

Advances in the technique of polymerization and catalysis has led to the possibility of obtaining many having improved physical and chemical properties of new polymers that can be used in a wide variety of excellent products and applications. The creation of new catalysts has enabled upon receipt of a specific polymer greatly expand the range of types of polymerization (solution, slurry, high pressure or gas phase). Advances in polymerization technology has also allowed us to develop more effective, efficient and economically superior ways. Illustration of these achievements, in particular, is the development of technology with the use of metallocene catalyst systems of the type with the bulky ligand. Despite these technological advances in polyolefin industry there are still common problems, as well as new when one task, associated with technological effectiveness. For example, when carrying out the process in the gas phase or slurry phase remains the problem of the tendency to impurities, formation of deposits or the generation of static electricity (in any combination).

During the well-known continuous gas-phase and slurry processes pollution and the formation of deposits on the walls of the reactor, which provide heat transfer, can lead to many technological problems. For example, a possible consequence of poor heat transfer during polymerization is sticking on the walls of the reactor polymer particles, which can continue to dry out the walls, which can lead to premature stopping of the reactor. In addition, depending on the conditions in the reactor, some portion of the polymer can be dissolved in the reactor diluent and re-deposited, for example on the surfaces of the metal heat exchangers, which also causes poor heat transfer and cooling.

In addition, the pollution, the formation of deposits or the generation of static electricity (or any combination) during the continuous gas-phase or slurry process can result in inefficient operation of various reactor systems. In case of pollution, education ExC is raised or the generation of static electricity effect, for example, the cooling mechanism of the recirculation system, the temperature sensors used for process control, or distribution plate (or simultaneously on several of them), this can lead to early stopping of the reactor.

In the art of the efforts of many specialists were sent to deal with the many problems of technological efficiency. For example, all US patents No. 4792592, 4803251, 4855370 and 5391657 discusses the technical means of reducing the generation of static electricity during the curing process introduction in the process, in particular, water, alcohols, ketones and/or inorganic chemical additives. In PCT publication WO 97/14721 from April 24, 1997, discusses the suppression of the education of little things that can cause the formation of deposits, adding to the reactor inert hydrocarbon. In US no 5627243 discussed a distribution plate of a new type for use in gas-phase fluidized bed reactor. In PCT publication WO 96/08520 discusses the possibility of exceptions added to the reactor cleanser. In US no 5461123 discusses the use of sound waves to reduce the formation of deposits. In US no 5066736 and EP-A1 0549252 discusses the introduction into the reactor moderator to reduce the formation of agglomerates. US No. 5610244 dedicated to the supply of fresh monomer in R. the actor directly above the layer to avoid contamination and to improve the quality of the polymer. In US no 5126414 discusses the implementation of the system of removal of oligomer to reduce contamination of the distribution plate and to provide polymers which are free from gels. In the application EP-A1 0453116, published on 23 October 1991, discusses the introduction into the reactor of antistatic agents to reduce the formation of deposits and agglomerates. In US no 4012574 discussed adding to the reactor surface-active compounds of perfluorocarbon number to reduce pollution. In US no 5026795 discussed adding in a polymerization zone of the reactor of antistatic together with liquid media. In US no 5410002 discusses the use of conventional catalytic system of the Ziegler-Natta-based titanium/magnesium on the media, where to reduce contamination of the selected antistatic agents are added directly to the reactor. In US no 5034480 and 5034481 discusses the reaction product with conventional titanium catalyst of the Ziegler-Natta with antistatic additives, to obtain ethylene polymers ultra-high molecular weight. In US no 3082198 discussed the introduction of a carboxylic acid, the amount of which depends on the amount of water in the polymerization of ethylene with the use of titanium/aluminum ORGANOMETALLIC catalysts in hydrocarbon liquid medium, and in US no 3919185 described suspension method using a non-polar hydrocarbon diluent and using the receiving conventional catalyst type Ziegler-Natta or type catalyst of the Phillips company and salts of polyvalent metal organic acid, molecular weight which is at least 300.

There are many other known methods of increasing the effectiveness of the process, including the coating on curing equipment, such as the processing of the walls of the reactor with the use of chromium compounds as described in US no 4532311 and 4876320; the introduction of various additives, such as, for example, said in PCT publication WO 97/46599 dated December 11, 1997, which discusses the introduction in the depletion zone of the polymerization reactor is not supported on a carrier soluble metallocene catalytic system and the introduction into the reactor protivoparazitarnymi or antistatic additives; the regulation of the rate of polymerization, in particular at the initial stage; and reflow reactor design.

In the description of other attempts in the art to improve the efficiency of the process, discussed the modification of the catalytic system using different ways to prepare the catalytic system. So, for example, designed in the art methods include the introduction of the components of the catalytic system in the composition in a specific order; the manipulation of the ratio of the various components of the catalytic system; varying the duration and/or temperature probe, or the combination of the project with the introduction of the components of the catalytic system in the composition; or just add in the catalytic system of various joints. These solutions and their combinations are discussed in the literature. Concrete illustrations in the art are separate techniques in the preparation and cooking techniques metallocene catalytic systems with the bulky ligand, more specifically applied to the media metallocene catalytic systems with the bulky ligand with reduced tendency to pollution and improved efficiency. Their examples include application WO 96/11961, published on 26 April 1996, in which as a component of the catalytic system on the media discusses the antistatic agent to reduce pollution and sedimentation during the process of polymerization in the gas, slurry or liquid medium; US patent No. 5283278 dedicated terpolymerization using metallocene catalyst or basic catalyst of the Ziegler-Natta in the presence of an antistatic agent; US patents No. 5332706 and 5473028, under which resort to special technology of preparation of the catalyst impregnated in the initial stage; US patents No. 5427991 and 5643847, which describes the chemical binding recoordination anionic activators media; US patent No. 5492975, which explains the polymer metallocene catalyst system; p is the tent US No. 5661095, in discussing the application of a metallocene catalyst for olefin copolymer and the unsaturated silane; PCT application WO 97/06186, published on 20 February 1997, in which we are talking about removing inorganic and organic impurities after preparation of the metallocene catalyst; PCT application WO 97/15602, published may 1, 1997, which discusses easily applied to the native metal complexes; PCT application WO 97/27224, published July 31, 1997 relating to the receipt supported on a carrier compound of the transition metal in the presence of unsaturated organic compounds containing at least one terminal double bond; and the application EP-A2 811638 discussing the use of metallocene catalyst and activating socializaton in the polymerization process in the presence of nitrogen-containing antistatic agent.

Although the use of all these possible solutions to the problem could, to a certain extent to reduce pollution or sedimentation, some roads in the implementation and/or do not allow to reduce pollution or the formation of deposits up to a level that is sufficient for successful continuous process, in particular industrial, large-scale process or combinations thereof.

When creating the present invention,it was found that the use of carboxylate metal salt in combination with supported on a carrier of the catalytic system, preferably metallocene catalytic system with a bulky ligand, preferably supported on a carrier metallocene catalytic system with the bulky ligand, significantly increases process efficiency (see, for example, the patent application US serial number 09/397409, filed September 16, 1999, and the patent application US serial number 09/397410 filed on 16 September 1999).

It is now established that the efficiency of the reactor can improve the connection of the new shared class in combination with the polymerization catalysts. Thus, the opportunity exists to develop a method of polymerization, which can be done by carrying out a continuous process with increased efficiency of the reactor and at the same time to get a new and improved polymers. Now you can also carry out continuous polymerization process with a more stable performance of the catalyst, with a weaker tendency to pollution/the formation of sediments and increased uptime.

The present invention offers a method of preparation of new and improved catalytic composition and its use in the polymerization process. This method involves the step of combining, contacting, mixing or blending (or their combination) katal the optical system, preferably supported on a carrier of a catalytic system, with gelatinizing agent. In one embodiment, the catalyst system comprises a catalytic compound of the usual type with a transition metal. In the most preferred embodiment, the catalytic system comprises a metallocene catalyst compound with the bulky ligand. The combination of catalytic systems and gelatinizing agent can be used in any process of polymerization of the olefin. The preferred polymerization processes are processes in the gas phase or in suspensioni phase, and the most preferred gas-phase process.

In another embodiment, the invention features a method of preparing a catalytic composition, which can be used for polymerization of olefin (olefin), and this method involves combining, contacting, mixing, or mixing (or combinations thereof) of the polymerization catalyst with at least one gelatinizing agent.

In one preferred embodiment, the object of the invention is a catalytic composition comprising a catalyst compound, preferably a catalytic compound of the usual type with a transition metal, more preferably a metallocene catalyst compound with a bulky ligand, activator or socatel the congestion (or combinations thereof), media and gelatinizing agent.

And yet, in another embodiment, the object of the invention is a method of polymerization of olefin (olefin) in the presence of a catalytic composition comprising a polymerization catalyst and gelatinizing agent, preferably the polymerization catalyst comprises a carrier, the preferred polymerization catalyst includes one or more catalytic compounds of the conventional type or metallocene catalyst compounds with bulky ligands or a combination thereof.

However, in another embodiment, the invention features a method of polymerization of olefin (olefin) in the presence of a catalyst of polymerization, the pre-merged entered into contact, mixed or blended with at least one gelatinizing agent.

The object of the invention is a method of preparation of the catalytic composition and the actual catalytic composition. The invention also relates to a polymerization process using such catalyst compositions characterized by improved efficiency and product characteristics. It was found that the result of applying gelatinizing agent in combination with a catalytic system is significantly improved polymerization process.

The General class of compounds, to the which you can use when performing the present invention, are gelatinizing agents, which are compounds capable of organic liquids (for example, in n-hexane) to form thermally reversible viscoelastic such liquids or similar solids materials (organogel). In other words, for compounds that can be used when implementing the invention, is characterized by the formation of organogels. Specifically organogel obtained by heating gelatinizing agents in organic liquids as long as they do not dissolve, and then, after dissolution, the solution containing gelatinizing agent, allowed to stand or to cool until then, until the gelatinization in which this agent is colloidal unit, which immobiliere in varying degrees the liquid.

For use in the method of polymerization according to the invention all acceptable polymerization catalysts, including catalysts conventional type with transition metals. But particularly preferred ways in which the use of metallocene catalysts with bulky ligands or connected by bridges with the bulky ligands (or combinations thereof). The following is a non-limiting description of various polymerization catalysts that can be used when implementing the invention.

Conventional catalysts with p is recognise metals are those traditional catalysts of Ziegler-Natta and chromium catalyst type catalyst of the Phillips company, which are well known in the art. Examples of conventional catalysts with transition metals are discussed in US№4115639, 4077904, 4482687, 4564605, 4721763, 4879359 and 4960741. Conventional catalytic transition metal compounds that can be used in the present invention include compounds of transition metals of groups III to VIII, preferably IVB through VIB, of the Periodic table of elements.

These conventional catalysts with transition metals can be represented by the formula MRxwhere M denotes a metal atom from groups IIIB to VIII, preferably from group IVB, more preferably titanium; R is a halogen atom or hydrocarbonaceous; and x represents the valence of the metal M. non-limiting examples of R include alkoxy, phenoxy, bromide, chloride and fluoride. Non-limiting examples of conventional catalysts with transition metals, in which M represents a titanium atom, include TiCl4, TiBr4, Ti(OS2H5)3CL, Ti(OS2H5)CL3, Ti(OS4H9)3CL, Ti(OS3H7)2CL2, Ti(OC2H5)2Br2, TiCl3·1/3ll3and Ti(OS12H25)CL3.

Catalytic transition metal compounds of the usual type based on magnesium/titanium electron-donor complexes that can be used is carried out according to the invention, presents, for example, in US No. 4302565 and 4302566. Particularly preferably derived MgTiCl6(ethyl acetate)4. In the application GB 2105355 describes the different catalytic vanadium compounds conventional type.

Conventional catalytic compounds of chromium, often called type catalysts catalysts of the Phillips company acceptable to use when performing the present invention include SGAs3chromatin, silylpropyl, chamillard (SGAs2CL2), chromium-2-ethylhexanoate, chromatiaceae [CR(ASAS)3] other non-limiting examples are given in US no 2285721, 3242099 and 3231550.

However, other conventional catalytic transition metal compounds and catalyst system suitable for use in the present invention, is presented in US no 4124532, 4302565, 4302566 and 5763723 and published applications EP-A2 0416815 and EP-A1 0420436.

Other catalysts may include cationic catalysts, such as ll3and other cobalt and iron catalysts are well known in the art.

These conventional catalytic transition metal compounds, in addition to some conventional chromium catalyst compounds are typically activated by one or more conventional socialization described below.

Normal Socialisticheskaya compounds for the above conventional is kataliticheskih of transition metal compounds can be represented by the formula in which M3denotes a metal atom of group IA, IIA, IIB or IIIA of the Periodic table of elements; M4denotes a metal atom of group IA of the Periodic table of elements; v represents a number from 0 to 1; each X2denotes the atom of any halogen; C denotes a number from 0 to 3; each R3denotes a monovalent hydrocarbon radical or a hydrogen atom; b represents a number from 1 to 4, and in which the difference (b minus equals at least 1. Other ORGANOMETALLIC Socialisticheskaya connection of conventional type for the above-mentioned catalysts conventional type with transition metals correspond to the formula M3R3kwhere M3denotes a metal atom of group IA, IIA, IIB or IIIA, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k, depending on the valency M3which in turn normally depends upon the particular group to which M3denotes 1, 2 or 3; and each R3may designate any monovalent hydrocarbon radical.

Non-limiting examples of ORGANOMETALLIC socialisticheskih compounds of General type with elements of groups IA, IIA, IIB and IIIA, which can be used in conjunction with the above described catalyst compounds of General type include motility, utility, DigiCert, butylamine, dieti the cadmium, basikali, diethylzinc, tri-n-butylamine, diisobutylamine, diethylcadmium, di-n-butylzinc and tri-n-amilor, especially aluminiumgie, such as tridecylamine, triethylaluminum, trimethylaluminum and triisobutylaluminum. Other Socialisticheskaya connection conventional type include monoethanolamine and hydrides of metals of groups IIA and mono - and diagonalalamanaly and hydrides of metals of groups IIIA. Non-limiting examples of such socialisticheskih compounds of General type include diisobutylaluminium, isobutylbarbituric, methylaniline, ActiveRecord, ethicallybased, diisobutylaluminium, methylmaleimide, diethylmaleate, getsilverlight, dipropylacetic, octylaniline, BUTYLCARBAMATE, dichlorophene, dibromopyridine and bromellite. ORGANOMETALLIC Socialisticheskaya connection conventional type specialists in this field known in the art, and a more complete discussion of these compounds can be found in US no 3221002 and 5093415.

Considering the purpose of the present description and attached claims, under conventional catalytic transition metal compounds excluded the metallocene catalyst compounds with bulky ligands, which are discussed below.

In General metallocene catalyst compounds with bulky the ligands include semi - and panoramaview connection contains one or more bulky ligands associated with at least one metal atom. Typical metallocene compounds with bulky ligands generally described as containing one or more bulky ligands and one or more leaving groups associated with at least one metal atom. In one preferred embodiment, at least one of the bulky ligands η -associated with the metal atom, most preferably η5-associated with the metal atom.

Bulky ligands are typically in the form of one or more disclosed, acyclic or condensed rings or ring systems, or combinations thereof. These bulky ligands, preferably ring or ring system, typically composed of atoms selected from atoms of elements of groups 13-16 of the Periodic table of elements, preferably the atoms are selected from a range, including carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron, aluminum and a combination thereof. The most preferred rings and ring systems consist of carbon atoms and are, in particular, although their list is not limited to, cyclopentadienyls ligands, ligand structure cyclopentadienyls type or other ligand structure with similar function, such as pentadienoic, qi is leachatecontaining and kidny ligands. Preferred metal atom selected from groups 3 to 15 and of the series of lanthanides and actinides of the Periodic table of elements. Preferred metal atom is a transition metal atom of group 4 to 12, more preferably groups 4, 5 and 6, and most preferably group 4.

According to one variant of metallocene catalyst compounds according to the invention with the bulky ligands correspond to the formula:

where M denotes a metal atom, which may relate to the metals of groups 3 through 12 of the Periodic table of elements or a series of lanthanides or actinides of the Periodic table of elements, and the preferred value of M is a transition metal atom of group 4, 5 or 6, more preferred value of M is a transition metal atom of group 4, and even more preferred value of M is an atom of zirconium, hafnium or titanium. Bulky ligands LAand LBare open, acyclic, or a condensed ring or ring system, which are ancillary ligand system consisting of unsubstituted or substituted cyclopentadienyls ligands or ligands cyclopentadienyls type heterocomplexes or heteroaromatics ligands cyclopentadienyls type or any combination of them. Neogen is to provide examples of bulky ligands include cyclopentadienyls ligands, cyclopentanophenanthrene ligands, Ingenierie ligands, benzydamine ligands, fluorenyl ligands, octahydrophenanthrene ligands, cyclooctatetraene ligands, cyclopentadecanone ligands, asenalnoye ligands, Solenoye ligands, pentalene ligands, vospolenie ligands, postinitialize (see WO 99/40125), pyrrolidine ligands, pyrazolidine ligands, carbazolyl ligands, brabanconne ligands and the like, and also include their hydrogenated versions, for example tetrahydroindole ligands. In one embodiment, LAand LBcan identify ligands of any other structures capable of forming with M η communication, preferably η3communication with M, and most preferably η5-communication. However, in another embodiment, the atomic molecular weight (Mw) LAor LBmore than 60 ated weight, preferably greater than 65 ated mass. In yet another embodiment, LAand LBcan include one or more heteroatoms, in particular nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination with the carbon atoms with the formation of open, acyclic, or preferably a condensed ring or ring system, for example heterocyclization auxiliary ligand. Other bulky ligands LAand LBinclude hot is their list is not limited to, bulky residues amides, phosphides, alkoxides, aryloxides, imides, carballido, ballidu, porphyrins, phthalocyanines, korinov and other polyazamacrocycles. Each of the LAand LBcan independently denote a bulky ligand of the same or another type that is associated with M. In one embodiment, in formula (I) contains only any one of the LAand LB.

Each of the LAand LBmay be independently unsubstituted or substituted by a combination of substitute groups R. non-limiting examples of substituting groups R include one or more groups selected from a hydrogen atom and linear and branched alkyl radicals and alkenyl radicals, etkinlik radicals, cycloalkyl radicals and aryl radicals, acyl radicals, aryl radicals, alkoxyalkyl, aryloxyalkyl, alkylthiomethyl, dialkylaminoalkyl, alkoxycarbonyl radicals, aryloxyalkyl radicals, carbamoyl radicals, alkyl - and dialkylammonium radicals, acyloxyacyl, acylaminoalkyl, railamerica, remotemachine, branched and cyclic alkilinity radicals, and combinations thereof. In a preferred embodiment, the replacement group R contains up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon atoms, which can also be substituted automaticlogin or heteroatoms. Non-limiting examples of alkyl substituents R cover of methyl, ethyl, through boutelou, pentelow, hexeline, cyclopentyloxy, tsiklogeksilnogo, benzyl or phenyl group, and include all their isomers, for example tertiary butyl, and isopropyl. Other gidrolabilna radicals include vermeil, foradil, defloratin, improper, bromhexin, chlorbenzyl and gidrokarbonatnye metalloorganic radicals including trimethylsilyl, trimethylgermyl and methyldiethylamine; glocalization metalloorganic radicals including Tris(trifluoromethyl)silyl, methylbis(deformity)silyl and bromomethylphenyl; and disubstituted boron radicals including, for example, Dimethylol; disubstituted pnictogens radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphinic; chalcogenide radicals, including hydroxy, ethoxy, propoxy, phenoxy, methylsulfinyl and ethylsulfinyl. For the non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, Germany, and also include olefins, such as, though not limited to, reinosapalencia deputies, including ligands with terminal vinyl, for example but-3-enyl, prop-2-enyl and Gex-5-enyl. In addition, at least two groups R, preferably two adjacent groups R, associated with the education of the ring structure, containing from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron and combinations thereof. Substituted group R, such as 1-butanol, with the metal atom M may form a carbon Sigma-bond.

With the metal atom M can be linked with other ligands, such as at least one leaving group Q. Bearing in mind the purposes of the present description and attached claims, the term "leaving group" is any ligand that can be split at the metallocene catalyst compounds with a bulky ligand, resulting in a metallocene catalyst cation with the bulky ligand capable of polymerization of one or more olefins. In one embodiment, Q represents monoanionic movable ligand that binds M a σ-bond. Depending on the oxidation state of the metal atom by the value of n is 0, 1 or 2, resulting in the above formula (I) displays a neutral metallocene catalyst compound with the bulky ligand.

Non-limiting examples of ligands Q include the remains weak bases, such as amines, phosphines, ethers, carboxylates, dieny, gidrolabilna radicals, each containing from 1 to 20 carbon atoms, hydrides, halogen atoms and a combination thereof. In another embodiment, two or the more the number of ligands Q form part of the condensed ring or ring system. Other examples of ligands Q include those substituents at R, which is shown above, including cyclobutenyl, tsiklogeksilnogo, Gately, colliny, triptorelin, tetramethylenebis, pentamethylenebis, metaliteracy, methoxy, ethoxy-, propoxy-, phenoxy-, bis(N-methylaniline), dimethylamine, dimethylphosphine radicals.

One of the options metallocene catalyst compounds with bulky ligand according to the invention include those compounds of formula (I)in which LAand LBinterconnected by at least one bridging group And, consequently, this formula takes the following form:

These are linked by the bridge compounds corresponding to the formula (II), known as the associated bridge metallocene catalyst compounds with bulky ligands. LALB, M, Q and n have the same meanings as above. Non-limiting examples of a linking bridge groups And include bridging groups containing at least one atom of group 13 to 16, often referred to as the divalent residues, such as, though not limited to, at least one of the carbon atoms, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin and a combination thereof. Preferred bridging group And includes a carbon atom, silicon or germanium, enableprefetcher group And includes at least one silicon atom or at least one carbon atom. Bridging group a may also include the replacement of the group R, which is shown above, including the atoms of halogen and iron. Non-limiting examples of bridging group a may be represented by the formula R'2C, R'2Si, R'2SiR'2Si, R'2Ge, R P, where R' independently denotes a radical, which represents the balance of hydride, hydrocarbon, substituted hydrocarbon, Halocarbon, substituted Halocarbon, gidrokarbonatnyj metalloorganicheskie balance, allocability metalloorganicheskie balance, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen atom, or two groups R' can be associated with the formation of a ring or ring system. One of the options associated bridges metallocene catalyst compounds of formula (II) with bulky ligands contain two or more bridging groups a (see EP-B1 664301).

One of the options metallocene catalyst compounds with bulky ligands are those compounds in which the substituents R bulky ligands LAand LBin formulas (I) and (II) is substituted by the same or different number of substituents at each of the bulky ligands. In another embodiment, the bulky ligands LAand LBin formulas (I) and (II) different.

Other metallocene catalytic connect the base and catalytic systems with bulky ligands, which can be used according to the invention include those listed in the US№5064802, 5145819, 5149819, 5243001, 5239022, 5276208, 5296434, 5321106, 5329031, 5304614, 5677401, 5723398, 5753578, 5854363, 5856547, 5858903, 5859158, 5900517, 5939503 and 5962718, in PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO 99/14221 and European publications EP-A 0578838, EP-A 0638595, EP In 0513380, EP-A1 0816372, EP-A2 0839834, EP-B1 0632819, EP-B1 0739361, EP-B1 0748821 and EP-B1 0757996.

In one embodiment, metallocene catalyst compounds with bulky ligands, which can be used according to the invention include metallocene compounds containing one bulky ligand with an associated bridge the heteroatom. Catalysts and catalytic systems of these types are represented, for example, in PCT publications WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO 96/00244, WO 97/15602 and WO 99/20637, in US№№5057475, 5096867, 5055438, 5198401, 5227440 and 5264405 and European publications EP-A 0420436.

Under this scenario metallocene catalyst compounds with bulky ligands correspond to the formula:

where M denotes a metal atom of groups 3 to 16 or metal atom selected from the ranks of actinides or lanthanides of the Periodic table of elements, and the preferred value of M is a transition metal atom of group 4 to 12, more preferred value of M is a transition metal atom of groups is 4, 5 or 6, and the most preferred value of M is a transition metal atom of group 4 in any oxidation state, especially titanium atom; LCdenotes a substituted or unsubstituted bulky ligand bound to M; J is associated with M; And is associated with LCand J; J denotes heteroaromatics ancillary ligand; And means bridging group; Q represents a monovalent anionic ligand; and n denotes an integer of 0, 1 or 2. In the above formula (III) LC, A and J form a condensed ring system. In one embodiment, in formula (III) LChas the same values as above for LAand a, M and Q in the formula (III) have the meanings indicated above for formula (I).

In the formula (III) J denotes heteroaromatics ligand, in which J denotes an element of group 15 with the coordination number of three or an element of group 16 of the Periodic table of elements with a coordination number of two. In a preferred embodiment, J contains an atom of nitrogen, phosphorus, oxygen or sulfur, with the most preferred nitrogen atom.

According to another variant of the metallocene catalyst compound with the bulky ligand is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted PI-bonded ligand, and one or some of heteroaryl residues, such as those presented in US no 5527752 and 5747406 and in EP-B1 0735057.

One of the options metallocene catalyst compound with the bulky ligand corresponds to the formula:

where M denotes a metal atom of groups 3 to 16, preferably a transition metal atom of group 4 to 12, and most preferably a transition metal atom of group 4, 5 or 6; LDdenotes a bulky ligand that is bound to M; each Q is independently associated with M, and Q2(YZ) forms a single shot polydentate ligand; a or Q denotes a monovalent anionic ligand, also associated with M; X denotes a univalent anionic group when n represents 2, or X denotes a divalent anionic group when n represents 1; n represents 1 or 2.

In the formula (IV), L and M have the meanings indicated above for formula (I); Q has the values specified above for formula (I), the preferred value of Q is chosen from the series comprising-O-, -NR-, -CR2- and-S-; Y denotes either C or S; Z is selected from a range, including-OR, -NR2, -CR3, -SR, -SiR3, -PR2, -H, substituted and unsubstituted aryl groups, provided that when Q represents-NR-, Z is selected from a range, including-OR, -NR2, -SR, -SiR3, -PR2and-H; R is selected from groups that include the atoms carbon, silicon, nitrogen, oxygen, and f is store or combinations thereof, moreover, the preferred value of R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably alkyl, cycloalkyl or aryl group; n denotes an integer from 1 to 4, preferably 1 or 2; X denotes a univalent anionic group when n represents 2, or X denotes a divalent anionic group when n denotes 1; the preferred value of X is urethane, carboxylate or other heteroallyl balance displayed by the combination of Q, Y, or Z.

In another embodiment, a catalytic metallocene compound type with bulky ligands represent a heterocyclic ligand complexes, bulky ligands, rings or ring systems which include one or more heteroatoms or a combination thereof. Non-limiting examples of heteroatoms include atoms of elements of groups 13 to 16, preferably the atoms of nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus and tin. Examples of such metallocene catalyst compounds with bulky ligands presented in WO 96/33202, WO 96/34021, WO 97/17379, WO 98/22486 and WO 99/40095 (decarbamoyl metal complexes), in EP-A1 and US 0874005№№5637660, 5539124, 5554775, 5756611, 5233049, 5744417 and 5856258.

In another embodiment, a metallocene catalyst compounds with bulky ligands are of FDS is th those complexes, which are known as catalysts with transition metals based on bidentate ligands containing pyridine or quinoline residues, such as those presented in the application U.S. serial number 09/103620, filed June 23, 1998, In another one embodiment, the metallocene catalyst compounds with bulky ligands are those which are presented in PCT publications WO 99/01481 and WO 98/42664.

In one embodiment, metallocene catalyst compound with the bulky ligand corresponds to the formula:

where M denotes a metal atom selected from groups 3 to 13 of the series of lanthanides and actinides of the Periodic table of elements; Q is associated to M and each Q denotes a monovalent, divalent or trivalent anion; X and Y are connected to M; one or more X and Y denote heteroatoms, preferably both X and Y denote heteroatoms; Y is contained in a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms, preferably from 2 to 30 carbon atoms; Z is related to X, where Z contains from 1 up to 50 non-hydrogen atoms, preferably from 1 to 50 carbon atoms, and in more preferred embodiment, Z represents a cyclic group containing 3 to 50 atoms, preferably from 3 to 30 carbon atoms; t represents 0 or 1; when t denotes 1, And indicates the bridging group is, associated with at least one of X, Y or J, preferably X and J; q represents 1 or 2; n represents an integer from 1 to 4 depending on the oxidation state M. In one embodiment, in which X denotes an oxygen atom or sulfur, fragment Z is optional. In another embodiment, in which X denotes a nitrogen atom or phosphorus, fragment Z is contained. One option preferred value of Z is an aryl group, more preferably a substituted aryl group.

In one embodiment, covered by the scope of the present invention, the metallocene catalyst compounds with bulky ligands include complexes Ni2+and Pd2+provided in the articles Johnson and others, "New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and α -Olifins", SOC. 1995, 117, 6414-6415 and Johnson and others, "Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium(II) Catalysts", SOC. 1996, 118, 267-268, and in applications WO 96/23010, published August 1, 1996, and WO 99/02472 and US No. 5852145, 5866663 and 5880241. These complexes can be either addition products dialkylamide ester or alkylated reaction products described dihalogenide complexes that can be activated by cationic States are described below activators of the present invention.

To metallocene catalyst compounds with bulky ligands are also those with the organisations of the metals of groups 8 to 10 ligands on diimino basis, presented in PCT publications WO 96/23010 and WO 97/48735 and in the work of Gibson and others, Chem.Comm., c. 849-850 (1998).

Other metallocene catalysts with bulky ligands are imagecomplete metals of groups 5 and 6 are shown in EP-A2 0816384 and US No. 5851945. In addition, metallocene catalysts with bulky ligands include bridge bizarrement compounds of metals of groups 4, represented in the work D.H.McConville and others in Organometallics 1195, 14, 5478-5480. In addition, associated bridges bisamine catalytic compounds presented in WO 96/27439. Other metallocene catalysts with bulky ligands represented as bis(hydroxyaromatic nitrogen-containing ligands) in US no 5852146. Another metallocene catalysts containing one or more atoms of elements in group 15 include those described in WO 98/46651. However, other metallocene catalysts with bulky ligands include those polycyclic metallocene catalysts with bulky ligands, as described in WO 99/20665.

In one embodiment, the list above described metallocene catalysts with bulky ligands provides for the inclusion of their structural, optical or enantiomeric isomers (meso and racemic isomers, see, for example, in US No. 5852143).

The above-described metallocene catalyst compounds with bulky ligands is typically activated in various ways to obtain catalytic compounds with free coordination site, which provides the coordination, implementation and polymerization of olefin (olefin).

Considering the purpose of the description of this application and the accompanying claims, the term "activator" is defined as referring to any compound, component, or method, the use of which provides the ability to activate any of the above-described metallocene catalyst compounds with bulky ligands or other catalytic compounds according to the invention. For non-limiting examples of activators include Lewis acid, recoordination ionic activators, ionizing activators and any other connections, including grounds Lewis, aluminiumgie, socializaton conventional type and combinations thereof that can convert a neutral metallocene catalyst compound with the bulky ligand in the catalytically active metallocene cation with the bulky ligand. The scope of the present invention covers the use of alumoxane or modified alumoxane as activator or also use ionizing activators, neutral or ionic, such as tri(n-butyl)ammoniates(pentafluorophenyl) boron, tripartitions metallosoderzhashhie predecessor and tripartitions metallomesogens the s predecessor, connection with polyhalomethanes heteroborane anions (see WO 98/43983) and their combinations that are sure to ionize the neutral metallocene catalyst compound with the bulky ligand.

One of the options there is also an activation method using ionizing ionic compounds not containing an active proton but capable of forming cation metallocene catalyst cation with the bulky ligand and coordinating anion, as described in EP-A 0426637 and EP-A 0573403 and US No. 5387568.

There are many ways to get alumoxane and modified alumoxanes, non-limiting examples of which are presented in US№4665208, 4952540, 5091352, 5206199, 5204419, 4874734, 4924018, 4908463, 4968827, 5308815, 5329032, 5248801, 5235081, 5157137, 5103031, 5391793, 5391529, 5693838, 5731253, 5731451, 5744656, 5847177, 5854166, 5856256 and 5939346 in European publications EP-A 0561476, EP-B1 0279586, EP-A 0594218 and EP-B1 0586665 and in PCT publication WO 94/10180.

Alyuminiiorganicheskikh compounds that can be used as activators include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylamine, tri-n-octylamine.

Ionizing compounds can include an active proton, or some other cation associated, but not coordinated or only loosely coordinated with the remaining ion of the ionizing compound. Such soy is inane described in European publications EP-A 0570982, EP-A 0520732, EP-A 0495375, EP-B1 0500944, EP-A-0277003 and EP-A 0277004, in US№№5153157, 5198401, 5066741, 5206197, 5241025, 5384299 and 5502124 and in the patent application US serial number 08/285380, filed August 3, 1994

Other activators include those compounds which are described in PCT publication WO 98/07515, such as Tris(2,2',2"-nonaboriginal)periluminal. The invention also provides the use of combinations of activators, such as combinations of alumoxanes with ionizing activators (see, in particular, EP-B1 0573120, PCT publication WO 94/07928 and WO 95/14044 and US No. 5153157 and 5453410). In WO 98/09996 described activation of metallocene catalyst compounds with bulky ligands by perchlorate, periodate and Iodate, including their hydrates. In WO 98/30602 and WO 98/30603 described the use of lithium(2,2'-biphenyldicarboxylic)-THF as activator for the metallocene catalyst compounds with bulky ligand. In WO 99/18135 described the use bioluminescence activators. In EP-B1 0781299 offered the use of sicilieweg salt in combination with coordinationin compatible anion. To convert a neutral metallocene catalyst compounds with bulky ligand or predecessor in connection with the metallocene cation and a bulky ligand capable of polymerization of olefins, provided the application activation methods using radiation (see application the R-B1 0615981), electrochemical oxidation and similar means known in the art. Other activators and methods of activating the metallocene catalyst compounds with bulky ligand represented, for example, in US No. 5849852, 5859653 and 5869723 and in WO 98/32775 and WO 99/42467 {[diastatochromogenes [Tris(pentafluorophenyl)borane]benzimidazole}].

Scope of the present invention includes a combination of one or more of the above-described metallocene catalyst compounds with bulky ligands or normal catalytic compounds with one or more activators or methods described above is activated.

The invention further provides for the possibility of combining other catalysts metallocene catalyst compounds with bulky ligands according to the invention (see, for example, US№4937299, 4935474, 5281679, 5359015, 5470811 and 5719241). Any of metallocene catalyst compounds with bulky ligands according to the invention it is also possible presence of at least one fluoride or fluoride leaving groups, as set out in the application U.S. serial number 09/191916, filed November 13, 1998

In another variant implementation of the invention, one or more metallocene catalyst compounds or catalyst systems with bulky ligands can be is used in combination with one or more catalyst compounds or catalyst systems of the conventional type. Non-limiting examples of mixed catalysts and catalytic systems are presented in US№№4159965, 4325837, 4701432, 5124418, 5077255, 5183867, 5391660, 5395810, 5691264, 5723399 and 5767031 and in PCT publications WO 96/23010 from August 1, 1996

The above-described metallocene catalyst compounds and catalyst systems with bulky ligands and catalyst compounds and catalyst system of the usual type with transition metals can be combined with one or more substrate materials or carriers using one of the methods applied on the media, well known in the art or as set forth below. In a preferred embodiment of the method according to the invention, the polymerization catalyst is used supported on a carrier form. For example, in the preferred embodiment, metallocene catalyst compound or catalyst system with the bulky ligand is supported on a carrier form, for example deposited on a substrate or carrier, in contact with it, embedded in it, adsorbed or absorbed in it.

The terms "substrate" and "carrier" are used interchangeably, they are applicable to any porous or non-porous substrate material, preferably to a porous substrate material, such as talc, inorganic oxides and inorganic chlorite is am. Other media include resinous materials of substrates, such as polystyrene, functionalized or crosslinked organic substrates, such as polystyrene-divinylbenzene, polyolefins and other polymeric compounds or any other organic or inorganic material, and mixtures thereof.

The preferred carriers are inorganic oxides that include the oxides of metals of groups 2, 3, 4, 5, 13 and 14. Preferred carriers include silica, alumina, kranidioti/aluminiumoxid, magnesium chloride and mixtures thereof. Other effective substrates include magnesium oxide, titanium dioxide, zirconium dioxide, montmorillonite. Can also be used in combination of substrate materials, such as kranidioti/chrome and kranidioti/titanpoker.

The preferred material of the carrier, most preferably an inorganic oxide, characterized by a specific surface area in the range from 10 to 700 m2/g and a pore volume in the range from 0.1 to 4.0 CC/g and an average particle size in the range from 10 to 500 μm. In a more preferred embodiment, the specific surface area of the substrate material is in the range from 50 to 500 m2/g and a pore volume ranging from 0.5 to 3.5 CC/g and average particle size is from 20 to 200 μm. In the most preferred embodiment, UD the global surface area of the substrate material is in the range from 100 to 400 m 2/g and the pore volume is from 0.8 to 3.0 CC/g and average particle size is from 20 to 100 μm. The average pore size of the carrier according to the invention typically is in the range from 10 to 1000 Å, preferably from 50 to 500 Å, and most preferably from 75 to 350 E.

Examples of application to the media metallocene catalytic systems with bulky ligands according to the invention are presented in US№4701432, 4808561, 4912075, 4925821, 4937217, 5008228, 5238892, 5240894, 5332706, 5346925, 5422325, 5466649, 5466766, 5468702, 5529965, 5554704, 5629253, 5639835, 5625015, 5643847, 5665665, 5698487, 5714424, 5723400, 5723402, 5731261, 5759940, 5767032 and 5770664, in patent applications US serial number 271598, filed July 7, 1994, and 788736, filed January 23, 1997, and publications PCT WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297.

Examples of application to the carrier of the catalytic systems of the conventional type according to the invention are presented in US№4894424, 4376062, 4395359, 4379759, 4405495, 4540758 and 5096869.

The possibility of application of metallocene catalyst compounds with bulky ligands according to the invention in conjunction with the activator on the same or a separate substrate or activator can be used in nenalezena media form, or may be deposited on a substrate different from a substrate on which is deposited metallocene catalyst compounds with bulky ligands according to the invention, or can use any combination of these options.

In the art of existence is Tvout various other methods of applying on the substrate a polymerization catalyst compound or catalyst system according to the invention. For example, the metallocene catalyst compound with the bulky ligand according to the invention can include associated with the polymer ligand, as described in US no 5473202 and 5770755; metallocene catalytic system with the bulky ligand according to the invention can be dried by spraying, as described in US no 5648310; the substrate used in combination with metallocene catalytic system with the bulky ligand according to the invention functionalitywith as described in European publication EP-A 0802203; or at least one Deputy or a leaving group chosen as described in US no 5688880.

In a preferred embodiment, the invention features deposited on a substrate metallocene catalytic system with the bulky ligand comprising a surface modifier, which is used in the preparation of the catalytic system on the substrate, as set forth in PCT publication WO 96/11960.

The preferred method of preparing a metallocene catalytic system with the bulky ligand on the media according to the invention described below, it can be found in patent applications US serial number 265533 filed June 24, 1994, and 265532, filed June 24, 1994, and PCT publications WO 96/00245 and WO 96/00243 from January 4, 1996, In this preferred method, the metallocene catalyst compound with the bulky ligand suspend the display in the liquid to obtain a solution metallocene and preparing a separate solution, comprising an activator and a liquid. As a liquid, you can use any compatible solvent or other liquid capable of forming with metallocene catalyst compounds with bulky ligands and/or the activator according to the invention the solution, or a combination of the two liquids. In the most preferred embodiment, as the liquid used cycloaliphatic or aromatic hydrocarbon, preferably toluene. Solutions metallocene catalyst compounds with a bulky ligand and activator are mixed and added to a porous substrate or the porous substrate is added to these solutions so that the total volume of the solution of metallocene catalyst compounds with a bulky ligand and activator solution or the solution of metallocene catalyst compounds with a bulky ligand and activator was less than five times the volume of pores of the porous substrate, more preferably less than four times, and even more preferably less than three times the volume; the preferred intervals range from 1.1 to 3.5 Krat, and most preferred is from 1.2 to 3 times.

Methods of determining the total volume of pores of the porous substrate in the art are well known. The details of one of these methods are discussed in volume 1 of the works of Experimental Methods in Catalytic Research (cademic Press, 1968) (see specifically c.67-96). This preferred method includes the use of a classical instrument BET to determine the absorption of nitrogen. Another method well known in the art, described in the work of Innes, Total Porosity and Particle Density of Fluid Catalysts by Liquid Titration, volume 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

The molar ratio between the metal of the activator component to the metal of the metallocene catalyst compounds with bulky ligands is in the range from 0.3:1 to 2000:1, preferably from 20:1 to 800:1, and most preferably from 50:1 to 500:1. When the activator is the ionizing activator such as activators based on anionic tetrakis(pentafluorophenyl)boron, the preferred molar ratio between the metal of the activator component and the metal component of the catalyst is in the range from 0.3:1 to 3:1.

One variant of execution of the invention before the main polymerization process in the presence of a metallocene catalyst system with the bulky ligand or catalyst conventional type with transition metal (or combinations thereof) according to the invention will terpolymeric olefin (olefin), preferably2-C30olefin (olefin or alpha-olefin (a-olefin), preferably ethylene or propylene, or combinations thereof. The process of terpolymerization can be periodic or nepreryvnym, it can be in gas, solution or slurry phase, including the creation of high blood pressure. Terpolymerization can be any olefin monomer, or combinations thereof in the presence of regulating the molecular weight of the agent, such as hydrogen. Examples of methods of terpolymerization can be found in US№№4748221, 4789359, 4923833, 4921825, 5283278 and 5705578, in European publication EP-0279863 and PCT publication WO 97/44371. Considering the purpose of the present description and attached claims, as a catalytic system for terpolymerization used catalytic system, deposited on a substrate.

When performing the invention compounds that can be used for combining, contacting or mixing (or combinations thereof) with a polymerization catalyst system in the present description generally designated as gelatinizing agents. Gelatinizing agents that can be used during execution of the invention, in organic liquids (for example, in n-hexane) are capable of forming thermally reversible viscoelastic such liquids or similar solids materials (organogel). Gelatinizing agents form organogel, when they are dissolved in the organic liquid and the solution is cooled (or give him to stand up) until then, until the gelatinization in which this agent is colloidal Assembly, which immobiliere in varying degrees the liquid.

Non-limiting examples gelatinizing agents or organizationsfrom with such characteristics include aluminum orthophosphate, steroid and antennae derivatives, gelatinization amino acid type, ORGANOMETALLIC compounds and Quaternary ammonium salt. One preferred gelatinizing agent is tetraoctylammonium.

Other gelatinizing agents include orthophosphate dihexadecyl, dimeny tetracarboxylate complex, steroid derivatives, such as desoxycholate, cholic, lithocholic acids and their salts, digitalinternetonline derivatives, such as 2,3-bis-n-decyloxybenzoate (BDOA) and related anthraquinone.

In the art as additives for polyolefins is also well-known cholesterol-4-(2-antioxi)butanoate and cholesterolenriched-2-carboxylate; ORGANOMETALLIC compounds such as diketonates and carboxylates of copper; salt, derivateservlet of sorbitol and polyols.

Other preferred gelatinizing agents include phosphate diepiriye compounds such as, for example, (OH)Al(ROPOR')2, (Et)Al(ROPOR')2, (Et)Al(ROPOR)2and Mg(ROPOR')2where R represents C12-20H21-37mainly With18H33, a R' of the means of CH 3.

In one embodiment, from among gelatinizing agents exclude salt of mono - or di-or tricarboxylic acid with a metal fragment from the Periodic table of elements.

The method of preparation of the catalytic composition in General includes combining, contacting, mixing, or mixing (or combinations thereof) catalyst system or polymerization catalyst with gelatinizing agent.

In one embodiment of the method according to the invention the catalyst is a conventional-type transition metal or metallocene catalyst with the bulky ligand (or combinations thereof) combine, enter in contact, mix, or a mix (or carry out a combination of these processes) with at least one gelatinizing agent. In the most preferred embodiment, the catalyst is a conventional-type transition metal or metallocene catalyst with the bulky ligand (or a combination of both) is applied to the substrate.

In another embodiment, the stage of the method according to the invention include the preparation of the polymerization catalyst, preferably a preparation applied on the substrate of the catalyst for polymerization, and the introduction of the polymerization catalyst in contact with at least one gelatinizing agent. In a preferred method, the catalyst for polymerization including the AET catalytic compound, the activator or acetalization and the substrate, and the preferred catalyst for the polymerization is a deposited on a substrate metallocene catalyst with the bulky ligand.

In one embodiment of the method according to the invention gelatinizing agent is introduced into contact with the catalyst system, preferably deposited on a substrate by the catalytic system, most preferably deposited on a substrate metallocene catalytic system with the bulky ligand, under conditions of normal temperature and pressure. In a preferred embodiment, the temperature probe when combined catalyst of polymerization and gelatinizing agent is in the range from 0 to 100° S, more preferably from 15 to 75° and the most preferred conditions are normal temperature and pressure.

In a preferred embodiment, the process of contacting the polymerization catalyst and gelatinizing agent is carried out in an atmosphere of inert gas, such as nitrogen. But the possibility of combining the catalyst for polymerization and gelatinizing agent in the presence of olefin (olefin), solvents and hydrogen.

In one embodiment, gelatinizing agent can be added at any stage during the preparation of the catalyst of polymerization.

In one variant of the implementation of the method according to the invention, the polymerization catalyst and gelatinizing agent are combined in the presence of a fluid, moreover, for example, this liquid may be mineral oil, toluene, hexane, isobutane or a mixture thereof. In a more preferred method gelatinizing agent is combined with a catalyst of polymerization, which is pre-cooked in a liquid, preferably in the form of a suspension, or combine with essentially dry or dried catalyst for the polymerization, which was previously placed in the liquid and re-suspended.

In one embodiment, the duration of contact gelatinizing agent and a catalyst of polymerization can be varied depending on one or more of the following conditions: temperature and pressure, type of mixing device, the number of components that must be combined, and even the mechanism of the combination catalyst of polymerization/gelatinizing agent in the reactor.

In a preferred embodiment, the polymerization catalyst, preferably a metallocene catalyst compound with a bulky ligand, and the substrate is introduced into contact with gelatinizing agent for a period of time from seconds to 24 hours, preferably from 1 min to 12 h, more preferably from 10 min to 10 h, and most preferably from 30 minutes to 8 hours

In one embodiment, the ratio between the mass gelatinizing agent and a catalytic mass connection with perehodnik metal is in the range from 0.01 to 1000, preferably in the range from 1 to 100, more preferably in the range from 2 to 50, and most preferably in the range from 4 to 20. In one embodiment, the ratio between the mass gelatinizing agent and a mass of catalytic compounds with transition metal is in the range from 2 to 20, more preferably in the range from 2 to 12, and most preferably in the range from 4 to 10.

In another embodiment of the method according to the invention the mass percentage gelatinizing agent, calculated on the total weight of the polymerization catalyst is in the range from 0.5 to 500 wt.%, preferably in the range from 1 to 25 wt.%, more preferably in the range from 2 to 12 wt.%, and most preferably in the range from 2 to 10 wt.%. In another embodiment, the mass percentage gelatinizing agent, calculated on the total weight of the polymerization catalyst is in the range from 1 to 50 wt.%, preferably in the range from 2 to 30 wt.%, and most preferably in the range from 2 to 20 wt.%.

In one embodiment of the method according to the invention is applied to the catalyst substrate of the usual type with a transition metal, preferably deposited on a substrate metallocene catalyst with a bulky ligand, galuut together with gelatinizing agent within such period, the time for which a significant portion deposited on a substrate of the catalyst is homogeneous miscible or substantially in contact (or both) with gelatinizing agent.

In a preferred embodiment, a catalytic system according to the invention is applied to the substrate, and in the preferred embodiment, deposited on a substrate catalytic system is essentially a dried, pre-cooked, almost dry or engineering. In a particularly preferred method according to the invention is pre-prepared, applied onto a substrate catalytic system is introduced into contact with at least one gelatinizing agent. This gelatinizing agent may be in solution or suspension or in the dry state, preferably gelatinizing agent is in a substantially dry or dried state. In the most preferred embodiment, gelatinizing agent is introduced into contact with the deposited on a substrate by the catalytic system, preferably deposited on a substrate metallocene catalytic system with a bulky ligand, a rotary mixer in a nitrogen atmosphere, and the most preferred mixer is a drum mixer, or in the process of mixing in the fluidized bed during the existence of the deposits which the polymerization catalyst and gelatinizing agent are in the solid state, i.e. they both are in essentially dry state or in a dried state.

In one embodiment of the method according to the invention the catalytic compound of the usual type with a transition metal, preferably a metallocene catalyst compound with a bulky ligand, enter into contact with the substrate with getting deposited on a substrate of catalytic compounds. In this method, the activator or acetalization for catalytic compound is introduced into contact with a separate substrate from getting deposited on a substrate activator or deposited on a substrate of socializaton. In this particular embodiment, the invention provides for subsequent mixing gelatinizing agent coated on the substrate by the catalytic compound or deposited on a substrate activator or catalyst in any order, a separate mixing mixing mixing mixing with only one deposited on a substrate by the catalyst or, preferably, deposited on a substrate activator before mixing with separately applied onto a substrate by the catalyst and the activator or socialization.

In one embodiment, the invention features a method of joint injection is not applied on the substrate of the catalyst for polymerization and gelatinizing agent in the reactor. In one of the variations is the polymerization catalyst used is not deposited on a substrate form preferably in liquid form, as described in US no 5317036 and 5693727 and European publications EP-A 0593083. The polymerization catalyst in liquid form can be sent with gelatinizing agent into the reactor using the injection methods described in PCT publication WO 97/46599.

When using a combination gelatinizing agent and is not deposited on a substrate metallocene catalytic system with the bulky ligand, the molar ratio between the metal of the activator component to the metal of the metallocene catalyst compounds with bulky ligand is in the range from 0.3:1 to 10,000:1, preferably from 100:1 to 5000:1, and most preferably from 500:1 to 2000:1.

The catalytic system on the media or the composition of the invention (or both), described above, are acceptable for use in any process of terpolymerization or polymerization (or in fact, and the other) in a wide range of temperatures and pressures. The temperature may be in the range from -60 to 280° C, preferably from 50 to 200° and the generated pressure can be in the range from 1 to 500 at or above.

Polymerization processes include processes in solution, gas phase, slurry phase, high pressure, and combinations thereof. Especially preferred is a polymerization in a gas phase or slurry phase one is whether multiple olefins, at least one of which is ethylene or propylene.

In one embodiment, the method according to the present invention is suitable for carrying out the polymerization process in solution, under high pressure, slurry or gas phase of one or more olefin monomers containing from 2 to 30 carbon atoms each, preferably from 2 to 12 carbon atoms, and more preferably from 2 to 8 carbon atoms. The invention is particularly well suited for the polymerization of two or more of such olefinic monomers as ethylene, propylene, butene-1, penten-1, 4-methylpentene-1, hexene-1, octene-1 and the mission-1.

Other monomers which may be used in the method according to the invention include ethylenevinylacetate monomers, diolefin containing from 4 to 18 carbon atoms each, paired and unpaired diene, polyene, vinyl monomers and cyclic olefins. Non-limiting examples of monomers that are suitable for use according to the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzoate, styrene, alkyl substituted styrene, ethylidenenorbornene, Dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the method according to the invention receive a copolymer of ethylene, and in this case, during the gas-phase process floor will marisoul ethylene and comonomer, representing at least one alpha-olefin containing from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms.

In another embodiment of the method according to the invention, the ethylene or propylene will polimerizuet with at least two other comonomers, one of which may (but not necessarily) be a diene, to obtain the ternary copolymer.

In one embodiment, the invention is applicable to the polymerization process, in particular for gas-phase or slurry process carried out in the polymerization of propylene, either individually or together with one or more other monomers, including ethylene or other olefins containing from 4 to 12 carbon atoms each (or combinations thereof). Polypropylene polymers may be produced using, in particular, connected by bridges metallocene catalysts with bulky ligands, as described in US no 5296434 and 5278264.

In the process of gas-phase polymerization typically use a continuous cycle, in which one part of the loop reactor system of the circulating gas stream, otherwise known as a recycle stream or pseudozyma environment, is heated in the reactor by the heat of polymerization. This heat away from the cycle of songs in another part of the cycle by means of the PTO cooling system outside the reactor. Typically, in gas-phase process for obtaining polymers with fluidized bed through a fluidized bed in the presence of catalyst under reaction conditions continuously circulates the gaseous flow comprising one or more monomers. This gaseous stream from the fluidized bed away and return to the reactor. At the same time from the reactor assign the polymer product, and instead of polymerized monomer add fresh monomer (see, for example, US№4543399, 4588790, 5028670, 5317036, 5352749, 5405922, 5436304, 5453471, 5462999, 5616661 and 5668228).

The pressure in the reactor during the gas-phase process can be varied from 100 psig (690 kPa) to 500 psig (3448 kPa), preferably in the range of from 200 psig (1379 kPa) to 400 psig (2759 kPa), more preferably in the range from 250 psig (1724 kPa) to 350 psig (2414 kPa).

The temperature in the reactor during the gas-phase process can be varied from 30 to 120° C, preferably from 60 to 115° S, more preferably in the range from 70 to 110° and most preferably in the range from 70 to 95° C.

Other gas-phase processes, for which it is intended the method according to the invention include polymerization processes with step-by-step or multi-stage processes. Methods for gas-phase processes, done by the means of which the invention is intended, include those presented in US no 5627242, 5665818 and 5677375 and European publications EP-A 0794200, EP-B1 0649992, EP-A 0802202 and EP-0634421.

In a preferred embodiment, the reactor used when performing the present invention and the method according to the invention provide the possibility of more than 500 lbs of polymer per hour (227 kg/HR) up to 200,000 lb/h (90900 kg/HR) or higher of polymer, preferably greater than 1000 lbs/HR (455 kg/HR), more preferably greater than 10,000 lbs/HR (4540 kg/HR), even more preferably more than 25000 lb/h (11300 kg/HR), still more preferably 35000 lb/h (15900 kg/h), however, even more preferably greater than 50,000 lbs/HR (22700 kg/HR)and most preferably greater than 65,000 lbs/HR (29000 kg/HR) to over 100,000 lb/h (45500 kg/h).

During the process of suspension polymerization usually create a pressure in the range from 1 to 50 at and even greater and temperatures in the range from 0 to 120° C. In the process of suspension polymerization, a suspension of solid powdered polymer is prepared in the liquid polymerization diluent, which is injected ethylene and comonomers and often together with the catalyst added hydrogen. The suspension comprising the diluent from the reactor periodically or continuously removed, after which the volatile components are separated from the polymer and optional after distillation return to the reactor. The quality is TBE liquid diluent in the polymerization environment typically use alkane, containing from 3 to 7 carbon atoms, preferably a branched alkane. The medium used in the polymerization conditions must be liquid and relatively inert. When using propane environment, the process should be carried out at a temperature and pressure above the critical parameters of the reaction diluent. The preferred media used is hexane or isobutane.

The preferred method of polymerization used in the implementation of the invention, referred to as polymerization in powdered form or by suspension polymerization, which support a lower temperature than that at which the polymer goes into solution. This method in the art are well known and described for example in US no 3248179. Other methods of suspension polymerization include those carried out with the use of a reactor with circulation, and methods using multiple reactors mixing, placed in series, parallel or a combination of these configurations. Non-limiting examples of suspension methods include ways reactor continuous circulation or mixing. There are also other examples of the suspension of the methods presented in US no 4613484.

In one embodiment, the reactor used in the suspension method according to the invention and the method according invented the Yu provides the possibility of obtaining more than 2000 lbs of polymer per hour (907 kg/h), more preferably greater than 5000 lbs/HR (2268 kg/HR)and most preferably greater than 10,000 lbs/HR (4540 kg/HR). In another embodiment, in a suspension reactor used in the method according to the invention, receive more than 15000 pounds of polymer per hour (6804 kg/HR), preferably from more than 25,000 lbs/HR (11340 kg/h) up to 100,000 lb/h (45500 kg/h).

Examples of methods implemented in the solution presented in US no 4271060, 5001205, 5236998 and 5589555 and PCT WO 99/32525.

B preferred variant of the method according to the invention process, preferably a slurry or gas phase process is carried out in the presence of a metallocene catalyst system with the bulky ligand according to the invention and in the absence or near absence of any cleansing supplements, such as triethylaluminum, trimethylaluminum, triisobutylaluminum, tri-n-hexylamine, diethylaluminium and dibutyltin. This preferred method is presented in PCT publication WO 9.6/08520 US and No. 5712352 and 5763543.

The polymers obtained according to the method according to the invention can be used in a wide variety of products and the ultimate goals of the application. The polymers obtained according to the method according to the invention include linear low density polyethylene, elastomers, plastomer, high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene and polypro the new copolymers.

Polymers, typically ethylene polymers on the basis of, have a density in the range from 0.86 to 0.97 g/CC, preferably in the range from 0.88 to to 0,920 g/CC, more preferably in the range from 0.900 for up to 0.96 g/CC, even more preferably in the range from 0,905 to 0.95 g/CC, more preferably in the range of from 0.910 to 0,940 g/CC, most preferably more 0,915 g/CC, more preferably 0,920 g/CC, and still more preferably more 0,925 g/scooter Density determined in accordance with ASTM D-1238.

The polymers obtained according to the method according to the invention generally have a molecular weight distribution, a ratio between srednevekovoi molecular weight and srednekamennogo molecular weight (Mw/Mn) of greater than 1.5 to 15, in particular from greater than 2 to 10, more preferably from more than about 2.2 to less than 8, and most preferably from 2.5 to 8.

The polymers according to the invention tend to have a narrow compositional distribution as determined by the measure of the width of the compositional distribution (PSCR). Additional details of determining PSCR copolymer specialists in this field known in the art (see, for example, PCT application WO 93/03093, published on February 18, 1993).

In one embodiment, such polymers obtained according to the invention with the use of the metallocene catalysts with bulky ligands, have PSCR, usually being in the range from greater than 50 to 100%, preferably 99%, preferably in the range from 55 to 85%, more preferably in the range from 60 to 80%, even more preferably greater than 60% and, more preferably more than 65%.

In another embodiment, such polymers produced using metallocene catalytic system with the bulky ligand according to the invention have PSCR less than 50%, more preferably less than 40%, and most preferably less than 30%.

In one embodiment, such polymers according to the present invention have a melt index (IL) or (I2), as it is defined under ASTM D-1238-E in the range from 0.01 to 1000 DG/min, more preferably from 0.01 to 100 DG/min, even more preferably from 0.1 to 50 DG/min, and most preferably from 0.1 to 10 DG/min

In one specific embodiment, the polymers according to the invention are characterized by the values of the ratio of the melt index (RD21/IL2) (RD21determined according to ASTM D-1238-F) of from 10 to less than 25, more preferably from 15 to less than 25.

In a preferred embodiment, the polymers according to the invention are characterized by the values of the ratio of the melt index (RD21/IL2) (RD21determined according to ASTM D-1238-F) of from preferably greater than 25, more preferably greater than 30, even more predpochtitelnye 40, however, even more preferably greater than 50, and most preferably more than 65. In another embodiment, the polymer according to the invention may have a narrow molecular weight distribution and compositional distribution, or Vice versa. Such polymers can be those presented in US no 5798427.

According to another variant according to the method according to the invention have the propylene polymers on the basis of. These polymers include atactic polypropylene, isotactic polypropylene, polisomaticheskoi and syndiotactic polypropylene. Other propylene polymers include propylene block - and high-impact copolymers. Propylene polymers of these types in the art are well known (see, for example, US No. 4794096, 3248455, 4376851, 5036034 and 5459117).

Proposed according to the invention polymers can be combined or ekstradiroval together with any other polymer. Non-limiting examples of other polymers include linear low density polyethylene obtained by catalysis using conventional catalysts of the Ziegler-Natta or metallocene catalysts with bulky ligands, or both in combination, elastomers, plastomer, polyethylene, high pressure low density polyethylene is high density and polypropylene.

The polymers obtained according to the method according to the invention, and with them the art can be used in such molding processes, as extrusion and co-extrusion films and sheets and spinning fiber, as well as blow molding, injection molding and rotary molding. Film materials include films made by extrusion injection blow and casting, film, produced jointly by the layer-by-layer extrusion or molding, which can be used as shrink film, cling film, stretch film, packing film for welding, oriented films, packaging for snacks, bags for harsh environments, bags for groceries, packaging for baked and frozen food packaging for medical purposes, sealing materials for industrial use, membranes used in contact and without contact with food products. The manufacture of fibers includes spinning from melt spinning from solution and the processes of spinning from the melt of the hollow fibers from the air stream for use in woven and non-woven forms in the manufacture of filter fabrics for towels, clothing for health care workers and geotextile materials. Extruded products include tubes for medical purposes, the coating of wires and cables, conventional pipes, geomembranes and facing materials for swimming pools. For molded products include single and multi-layer products in the form of bottles, largest the overall capacity, large hollow articles, rigid containers for food and toys.

EXAMPLES

For a better understanding of the present invention, including describing the advantages, the following examples.

Example 1

The preparation of the catalyst And

A 2-gallon (EUR 7.57 l) reactor was loaded 1060 g of the solution methylalumoxane (MAO) in toluene, available on the company Albemarle Corp., Baton Rouge, PCs Louisiana, concentration of 30 wt.%, and then 1.5 l of toluene. With stirring the reactor was added to 19.8 g dimethylsilane-bis(tetrahydroindene)zirconiated, metallocene with the associated bridge bulky ligand, in the form of a solution in toluene concentration of 8 wt.% and at room temperature the mixture was stirred for 60 min, receiving a pre-mixed catalytic solution. Later in this pre-mixed solution in the reactor slowly, in stages, one third of the added silica dehydrated at 600° available on the company Crosfield Limited, Warrington, England. The mixture was stirred at room temperature for 20 min, after which the reactor was added 24 g of the product Kemamine AS-990 [which corresponds to the formula (C18H37NCH2CH2OH)2and available on the company Witco Corp., Memphis, PCs tn] in the form of a toluene solution with a concentration of 10 wt.% and stirring continued p and room temperature for 30 minutes Then the temperature was raised to 68° (155° F) and applied vacuum target dry curing catalyst. The drying was continued at low speed mixing for about 6 hours, up until the catalyst is not subjected to engineering. After that it was unloaded into the flask and kept in a nitrogen atmosphere. Due to some losses in the process of drying, the yield was around 1050 According to the analysis, this catalyst consisted of 0.32 wt.% Zr and 11.8 wt.% Al.

Comparative example 2 (DSS 2)

The polymerization process

A 2-liter autoclave reactor in a stream of nitrogen was loaded as a means of purification from impurities 0.16 mmole of triethylaluminum (TEAL), and then 25 CC of 1-hexene as co monomer and 800 CC of isobutane diluent. The contents of the reactor were heated to 80° C, after which the reactor was added 100 mg deposited on silica catalyst prepared as described in example 1 (catalyst A), mixed with 10 CC of hexane. The mixture of the catalyst hexane was introduced into the reactor simultaneously with ethylene so that the total gauge pressure in the reactor reached 325 psi (2240 kPa). The temperature of the reactor was maintained at a level of 85° and polymerization was performed for 40 min after 40 min, the reactor was cooled, ethylene dumped into the atmosphere and the reactor was opened. The walls of reactor blade stirrer was examined for the presence of polymer deposits, and depending on the amount of polluting material, the catalyst was assigned a score on a scale from 0 to 6, where a score of 0 meant the absence of contaminating material in the examination of the walls of the reactor and the agitator blades, and a score of 6 meant that all polymer granules or particles deposited on the walls of the reactor or the blades of the mixer (i.e. particle engineering polymer was absent).

Example 2

The experiment of example 2 was carried out similarly to comparative example 2 (DSS 2) with the following exceptions. Before adding to the reactor a catalyst And with 100 mg of catalyst a and 10 CC of hexane was mixed 1 mg (1 wt.% in terms of the weight of the loaded catalyst) tetraoctylammonium, organic gelatinizing agent. Then this mixture was introduced into the reactor simultaneously with the filing of ethylene and the reaction was carried out similarly to comparative example 2.

As shown in table 1, in the absence of organizationsfor the reactor was found to be highly contaminated, while in the presence of organizationsfor received engineering granules and deposits on the walls were missing.

Table 1
ExampleGelatinizing agentThe number used gelatinizing agentAssessment of the extent and pollution Notes
AB 2No04Extensive polymer deposits on the walls and stirrer
2Tetraoctyl monobromide1 mg0The lack of sediments/contaminants on the walls or mixer

Examples 3 through 6 and comparative examples 3 through 9

During the other evaluation experiments studied several materials in order to install, have properties gelatinizing agent. Characteristics gelatinizing agent was determined by dissolving 2 wt.% each relevant material in 50 ml of n-hexane with stirring at room temperature or at elevated temperature up to 100° With its speed increased by 5° C. After dissolution, the mixture was allowed to stand at room temperature or with cooling to room temperature without stirring for 5 min and then immediately examined on the subject of gelatinization, i.e. a mixture of different visually studied on the formation of colloidal dispersions possessing characteristics similar viscoelastic liquids or similar solids content.

Once established, are different materials properties gelatinizing agent, these materials assessment is ivali to their respective influence on the performance of the reactor in accordance with the methodology set forth above in example 2. For this assessment was repeated the experiment of comparative example 2 this experiment was designated as comparative example 3 (FRS 3). The characterization data gelatinizing agent and assess the performance of the reactor is shown below in table 2.

The data in table 2 show that some materials exhibit characteristics gelatinizing agent, while others are not. The data in table 2 also show that although some materials do not exhibit characteristics gelatinizing agent (i.e. are "degelatinised materials"), they, nevertheless, provide enhanced protection of the reactor against pollution (see DSS 5 and 6), while the other degelatinised materials significantly improved protection is not provided (see AB 7 to 9). And finally, as it has been unexpectedly found, the data in table 2 show that all materials that exhibit characteristics gelatinizing agent, therefore provides significantly improved protection of the reactor against pollution (i.e. the assessment of the degree of contamination was less than 2.0). Thus, to ensure appropriate substantially improved protection of the reactor against pollution or sedimentation, or from either of these you must use at least one gelatinizing agent in combination or in MESI with a polymerization catalyst system or any combination of them. This gelatinizing agent can be combined, to enter into contact or mixed with a polymerization catalyst system before or after introduction into the reactor, but in the preferred embodiment, it is their combination, introduction to the contact or mixture, or any Association is carried out before introduction into the reactor.

Although the present invention is presented and illustrated with reference to specific embodiments of the for the usual experts in the field of technology is apparent that the invention leads to variants, which in the present description it is not necessary to illustrate. For example, you can add gelatinizing agent into the reactor in addition to its introduction into contact with a catalytic system according to the invention. For these reasons, in order to determine the actual scope of the present invention should be handled only by the attached claims.

(OH)Al(ROPOR')2
Table 2
ExamplesMaterialsProperties gelatinizing agentProtection of the reactor against pollution degreeEvaluation of pollution degree
AB 3NoNPNP5
PR 3YesYes0,5
PR 4(Et)Al(ROPOR')2YesYes1
PR 5(Et)Al(ROPOR)2YesYes0,25
PR 6Mg(ROPOR')2YesYes0,25
SRC 4ROPOR'NoNo3
AB 3(Bu)Mg(ROPOR')NoYes0,5
AB 6(Et)2Al(ROPOR')NoYes0,5
AB 7Zn(ROPOR')2NoNo2,5
AB 8(Et)Zn(ROPOR')NoNo2
AB 9Product Fe3O4+ ROPOR'No, only the thickeningNo2,5

1. The catalytic composition which is a composition prepared from a polymerization catalyst system and at least one gelatinizing agent, in which gelatinizing agent is chosen from the group comprising diepiriye phosphates, steroid and antilove derivatives,gelatinization amino acid type and tetraoctylammonium, and in which the polymerization catalyst system selected from the group consisting of catalytic compounds of General type with transition metal metallocene catalyst compounds.

2. The catalytic composition according to claim 1, in which gelatinizing agent selected from the group including orthophosphate dihexadecyl, 2,3-bis-n-decyloxybenzoate, 2,3-bis-n-dellagiarino, cholesteryl-4-(2-antioxi)butanoate, (OH)Al(ROPOR')2, (Et)Al(ROPOR')2, (Et)Al(ROPOR)2, Mg(ROPOR')2where R means12-20H21-37and R' is CH3and cholesterolenriched-2-carboxylate.

3. The catalytic composition according to claim 1, in which the polymerization catalyst is a deposited on a substrate, the polymerization catalyst comprising a substrate, and where the specified substrate is chosen from the group comprising talc, inorganic oxides and inorganic chlorides.

4. The catalytic composition according to one of the preceding paragraphs, in which gelatinizing agent excludes salt of mono-, or di-or tricarboxylic acid with a metal fragment from the Periodic table of elements.

5. The method of preparation of the catalytic composition, comprising the following stages:

(a) obtaining a catalyst of polymerization and

(b) adding at least one gelatinizing agent, where W is lotensinbuy agent selected from the group including diepiriye phosphates, steroid and antilove derivatives, gelatinization amino acid type and tetraoctylammonium, and in which the polymerization catalyst is chosen from the group consisting of catalytic compounds of General type with transition metal metallocene catalyst compounds.

6. The method according to claim 5, in which the polymerization catalyst includes a substrate.

7. The method according to claim 5, where gelatinizing agent excludes those salts which are salts of mono-, or di-or tricarboxylic acid with a metal fragment from the Periodic table of elements.

8. Method for continuous polymerization of olefin monomer (monomers) in the reactor at polymerization conditions, and this method includes the following stages:

(a) introducing into the reactor olefin monomer (monomers);

(b) introducing into the reactor the polymerization catalyst system and at least one gelatinizing agent and

(C) removing from the reactor the polymer product,

in which gelatinizing agent is chosen from the group comprising diepiriye phosphates, steroid and antilove derivatives, gelatinization amino acid type and tetraoctylammonium, and in which the polymerization catalyst is chosen from the group consisting of catalytic compounds as the nogo-type transition metal metallocene catalyst compounds.

9. The method according to claim 8, in which the process is a suspension process.

10. The method according to claim 8, in which the process is a gas phase process.

11. The method according to claim 8, in which gelatinizing agent is introduced into contact with a polymerization catalyst system prior to its introduction into the reactor.

12. The method of claim 8, where gelatinizing agent excludes those salts which are salts of mono-, or di-or tricarboxylic acid with a metal fragment from the Periodic table of elements.

13. Method for continuous gas-phase polymerization of the monomer (monomers) in a reactor, comprising the following stages:

(a) introducing into the reactor recycle stream, and the recycle stream comprises one or more monomers;

(b) introducing into the reactor the polymerization catalyst system and at least one gelatinizing agent;

(C) removing from the reactor recycle stream;

(d) cooling the recycle stream;

(d) re-introduction into the reactor recycle stream;

(e) introducing into the reactor additional monomer (monomers) to replace the polymerized monomer (monomers) and

(g) removing from the reactor the polymer product,

in which gelatinizing agent is chosen from the group comprising diepiriye phosphates, with araignee and antilove derivatives, gelatinization amino acid type and tetraoctylammonium, and in which the polymerization catalyst is chosen from the group consisting of catalytic compounds of General type with transition metal metallocene catalyst compounds.

14. The method according to item 13, in which gelatinizing agent is introduced into contact with the polymerization catalyst prior to its introduction into the reactor.

15. The method according to item 13, in which the polymerization catalyst includes a substrate.

16. The method according to item 13, where gelatinizing agent excludes those salts which are salts of mono-, or di-or tricarboxylic acid with a metal fragment from the Periodic table of elements.

17. Method for continuous gas-phase polymerization of ethylene and one or more alpha-olefins containing 4 or more carbon atoms, under a gauge pressure in the range from 200 to 400 psig (1379 to 2759 kPa) and the temperature of polymerization in the range from 70 to 110°With, in the performance of more than 10,000 pounds (4540 kg) of polymer product per hour and when the performance of the catalyst for polymerization of more than 1500 g of polymer product per gram of catalyst of polymerization, and this process is carried out in the presence of at least one gelatinizing agent.



 

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