Catalytic composition and its preparation and use in the polymerization process

 

(57) Abstract:

In the application described catalytic composition and method of preparation of this catalytic composition of the polymerization catalyst and the carboxylate metal salt. It also describes the use of this catalyst composition in the polymerization of olefins. Such a polymerization catalytic system, in particular, applied to the media. More specifically, the polymerization catalyst includes a catalytic system of the metallocene type with the bulky ligand and the carboxylate metal salt, which corresponds to the formula: MQx(OOCR)y,where M denotes a metal atom of group III of the Periodic table; Q denotes hydroxyl; R is a hydrocarbon radical containing 2-100 carbon atoms; x denotes an integer of 1 or 2, y represents an integer of 1 or 2, and the sum of x and y is equal to the valence of the metal, and the content of the carboxylate metal salt, calculated on the total weight of the polymerization catalyst is in the range of 0.5 to 100 wt.%. The claimed invention allows for continuous polymerization process in a more stable performance of the catalytic system, low tendency to dirty the Ü TECHNOLOGY, The INVENTION RELATES

The present invention relates to catalytic compositions and methods of preparation of this catalyst composition and to its use in the polymerization of olefins. The object of the present invention is, in particular, the method of preparation of the catalytic composition metallocene catalytic system of the type with the bulky ligand and/or catalyst system of the usual type with a transition metal and a carboxylate metal salt.

BACKGROUND of INVENTION

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. Development of new catalysts has greatly expand the range of types of polymerization (solution, slurry, high pressure or gas phase) upon receipt of a specific polymer. Advances in polymerization technology has also allowed us to develop more effective, efficient and economically superior ways. Illustration of these Costigan Emistim ligand. Despite these technological advances in polyolefin industry there are still common problems, as well as new challenges related to the effectiveness of the technology. For example, during the processes in the gas phase or slurry phase remains a problem, due to the tendency to contamination and/or the formation of deposits.

For example, in a continuous slurry process, the contamination of the surface of the walls of the reactor, which provide heat transfer, can lead to many technological problems. The result of poor heat transfer during polymerization may be the sticking of polymer particles on the walls of the reactor. Such polymer particles 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 metal heat exchangers.

In a typical continuous gas-phase processes for many reasons, including the heat released during polymerization, use of the recirculation system. Pollution, education is about process can result in inefficient operation of various reactor systems. In the case of influence, for example, the cooling mechanism recirculation system temperature sensors used for process control, and distribution plate that can lead to early stopping of the reactor.

Taking into account the evidence of this, the efforts of many experts in the art have been directed to the solution of 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 added 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 CE fresh monomer to the reactor 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 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 coating 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, in PCT publication WO 97/46599 dated December 11, 1997, which discusses the introduction in the depletion zone of the polymerization reactor soluble metallocene catalytic system of the type without the media 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 the other attempts in the art, taken to improve the effectiveness 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 catalyt the catalytic system in the song and 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 methods of preparation of metallocene catalyst systems of the type with a bulky ligand, more specifically applied to the media metallocene catalytic systems of the type 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 to 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, where describes the chemical binding recoordination anionic activators media; US patent No. 5492975, which explains the polymer metallocene catalytic system Assenova silane as a carrier; PCT application WO 97/06186, published on 20 February 1997, where we are talking about removing inorganic and organic impurities after preparation of the metallocene catalyst type; 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, at the end of the molecule which contains at least one double bond; and the application EP-A2 811638, discuss 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 may not lead to the reduction of pollution or sedimentation to a level that is sufficient for successful continuous process, in particular industrial or large-scale process.

Thus, there is petroproduccion operability of the reactor and at the same time obtaining new and improved polymers. There is also a great need for the development of the method of carrying out continuous polymerization process in a more stable performance of the catalyst, low tendency to pollution/the formation of deposits and increased the duration of the process.

SUMMARY of the INVENTION

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, blending and/or alignment of the catalytic system, preferably the catalytic system on the media, with a carboxylate metal salt. In one embodiment, the catalyst system comprises a catalytic compound of a transition metal of conventional type. In the most preferred embodiment, the catalytic system includes a catalytic metallocene compound type with the bulky ligand. The combination of the catalytic system and the carboxylate metal salt can be used in any process for the polymerization of olefins. Preferred polymerization processes are processes in gas phase and slurry phase, most predpochtite eticheskoi composition, which can be used for polymerization of olefin (olefin), and this method involves combining, contacting, blending and/or a combination of a polymerization catalyst with at least one carboxylate metal salt. In one embodiment, the curing catalyst is a polymerization catalyst conventional type based on the transition metal, more preferably supported on a carrier of a polymerization catalyst usual type based on a transition metal. In the most preferred embodiment, the polymerization catalyst is a metallocene catalyst of the type with a bulky ligand, preferably a polymerization catalyst metallocene type with the bulky ligand supported on a carrier.

One of the options 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 catalytic metallocene compound type with the bulky ligand, the activator and/or socialization, the media and the carboxylate metal salt.

In the preferred FPIC is more preferably mixed in a dry state or pseudogout with a catalytic system on the media or the curing catalyst, including the media. In this most preferred embodiment, the polymerization catalyst comprises at least one catalytic metallocene compound type with the bulky ligand, the activator and the media.

Alternatively 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 a carboxylate metal salt. Preferred polymerization catalyst comprises a carrier, a preferred polymerization catalyst includes one or more combinations of the catalytic compounds of the usual type and/or catalytic metallocene compound type with the bulky ligand.

In a preferred variant of the method of preparation of the catalytic compositions according to the invention, this method comprises the stage of combining the catalytic metallocene compound type with the bulky ligand, activator and media getting metallocene catalytic system of the type with the bulky ligand on the media and contacting this catalytic metallocene compound type with the bulky ligand on the media with a carboxylate metal salt is om on the media and the carboxylate metal salt are practically in a dry state or in a dried state.

In one embodiment, the invention features a method of polymerization of olefin (olefin) in the presence of a polymerization catalyst which is incorporated entered into contact, combined or mixed with at least one carboxylate metal salt.

DETAILED description of the INVENTION

INTRODUCTION

The object of the invention is a method of preparation of the catalytic composition and the catalytic composition. According to the invention there is a method of polymerization, characterized by increased efficiency and productivity, using the catalytic composition. It was found that the use of carboxylate metal salt in combination with a catalytic system leads to a significant improvement in the polymerization process. Especially surprising is the effect achieved when the catalytic system is applied to the media, more unexpected effect achieved when the catalyst system is a catalyst system of the metallocene type with the bulky ligand, and another unexpected effect of the very high activity of the catalysts of the metallocene type with the bulky ligand and/or the introduction of large quantities of comonomeric links.

Even more unexpected was the possibility of a polymerization process with improved efficiency of polymers with a fractional melt index and higher density with a combination of a polymerization catalyst and a carboxylate metal salt. This discovery was especially important because in the polymer industry is well known that taking into account the efficiency of the process, obtaining polymers of these types associated with problems of a technological nature.

The result of applying the following polymerizations, a significant decrease in sedimentation and pollution, improved performance of the catalyst improved the morphology of the polymer particles without undesirable effects on the physical properties of polymers and the possibility of obtaining polymers over a wide range.

CATALYST COMPONENTS AND CATALYST SYSTEM

For use in the method of polymerization according to the invention all acceptable polymerization catalysts, including catalysts conventional type with transition metals. However, during particularly preferred metallocene catalysts of the type with the bulky ligand and/or with the associated bridge bulky ligand. The following is a non-limiting discussion of various polymerization catalysts that can be used when implementing the invention.

The catalysts of conventional type with transition metals

Catalysts conventional type with transition metals are traditional catalysts of Ziegler-Natta and chromium catalyst type catalyst of the Phillips company, well known in the art. Examples of catalysts of conventional type with transition metals are discussed in the patents US the links. Catalytic transition metal compounds of the usual type, which can be used in the present invention include compounds of transition metals of groups III to VIII, preferably IVB-VIB, of the Periodic table of elements.

These catalysts conventional type 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 catalysts of conventional type 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(OS2H5)Br2, Ti(CL3·1/3ll3and Ti(OC12H25)C13.

The catalytic compounds of chromium conventional type based on magnesium/titanium electron-donor complexes, which can be used according to the invention is represented, for example, in US patents No. is derived giCl6(ethyl acetate)4. In the application GB 2105355 included in the present description by reference, presents various catalytic vanadium compounds of the usual type. Non-limiting examples of catalytic vanadium compounds of General type include analyticaland-alkoxyalkane and alkoxides, such as Vl3, VOCl2(OBu) where VI denotes butyl, and VO(OS2H5)3; undeteriorated and canadiancontrolled, such as VCl4and VCl3(OBu); vanadium and venodilatation and chloroacetoacetate, such as V(ASAS)3and VOCl2(AcAc), where (ASAS) denotes acetylacetonate. The preferred catalytic vanadium compounds of the usual type are Vl3, VCl4and VOCl2-OR, where R is a hydrocarbon radical, preferably aliphatic or aromatic hydrocarbon WITH1-C10radical, such as ethyl, phenyl, isopropyl, butyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, naphthyl, etc. and canadianamerican.

Catalytic transition metal compounds of the usual type, often referred to as compounds of the type catalysts of the Phillips company, acceptable for use in vypolnim-2-ethylhexanoate, chromatiaceae [CR(ASAS)3] and so on, non-limiting examples are presented in US patents No. 2285721, 3242099 and 3231550, which are not fully included in the present description as a reference.

However, other catalytic compounds of transition metals of conventional type and of a catalytic system suitable for use in the present invention, is presented in US patents No. 4124532, 4302565, 4302566 and 5763723 and published applications EP-A2 0416815 and EP-A1 0420436, and they are all included in the present description as a reference. The catalysts of conventional type with transition metals according to the invention can also reply to the formula M'tM"X2tYuE, where M' represents Mg, Mn and/or CA; t represents a number of 0.5 to 2; M represents a transition metal atom of Ti, V and/or Zr; X denotes a halogen atom, preferably CL, Br or I; each Y, which may be the same or different, represents a halogen atom alone or in combination with an oxygen atom, -NR2, -OR, -SR, -COOR, or-OSOOR, where R is a hydrocarbon radical, in particular alkyl, aryl, cycloalkenyl or arylalkyl radical, acetylacetonate anion in an amount which satisfies the valence state of M'; and denotes a number from 0.5 to 20; E is denoted by the o acids; (b) alcohols; (C) ethers; (g) amines; (e) esters of carbonic acid; (e) nitrile; (g) phosphoramide; (C) esters of phosphoric and phosphorous acids and (K) of phosphorus oxychloride. Non-limiting examples of complexes corresponding to the formula above, include MgTiCl5·2CH3COOC2H5, Mg3Ti2Cl12·7CH3COOC2H5, MgTiCl5·6C2H5OH, MgTiCl5·100CH3OH, MgTiCl5·(tetrahydrofuran), MgTi2Cl12·7C6H5CN, Mg3Ti2Cl12·6C6H5COOC2H5, MgTiCl6·2CH3COOC2H5, MgTiCl6·6C5H5N, MgiCl5(OCH3)·2CH3SOOS2H5, MgTiCl5N(C6H5)2·3CH3COOC2H5, MgTiBr2Cl4·2(C2H5)2O, MnTiCl5·4C2H5OH, SB3V2CL12·SN3SOOS2H5, MgZrl6·4(tetrahydrofuran). Other catalysts may include cationic catalysts, such as ll3and other cobalt and iron catalysts are well known in the art.

These catalytic compounds of transition metals of conventional type, except for some chrome-containing catalytic compounds is below.

Socializaton conventional type

Socialisticheskaya connection of conventional type for the above-mentioned catalytic transition metal compounds of the usual type may be represented by the formula M3M4vX2cR3b-C in which M4denotes 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 denotes the number 0 to 1; each X2denotes the atom of any halogen; C indicates the number of 0-3; each R3denotes a monovalent hydrocarbon radical or a hydrogen atom; b represents the number of 1-4, 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 metal 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 in accordance with the valency of M3which in turn normally depends upon the particular group to which M3denotes 1, 2 or 3; and each R3may designate any odka compounds of elements of groups IA, PA and IIIA of conventional type, which can be used in conjunction with the above described catalyst compounds of General type include motility, utility, DigiCert, butylamine, diethylcadmium, 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, for a more complete discussion of these compounds can be found in US patents No. 3221002 and 5093415, which is asego description and the accompanying claims, from the list of catalytic transition metal compounds of the usual type excluded the catalytic metallocene compound type with the bulky ligand, which are discussed below. Given the purpose of the present description and attached claims, the term "socialization" is used to denote socialization conventional type or ORGANOMETALLIC socialisticheskih compounds of General type. Catalytic metallocene compound type with the bulky ligand and catalytic systems intended for use in combination with a carboxylate metal salt according to the invention, described below.

Catalytic metallocene compound type with the bulky ligand In the overall catalytic metallocene compound type with the bulky ligand include semi - and panoramaview compounds containing one or more bulky ligands, including patterns cyclopentadienyls type and other similar functional structures, such as pentadiene, cyclopentadienyl and imides. Typical metallocene compound type with the bulky ligand is usually described as containing one or more ligands capable of forming with the atom transition maturehotel metal, selected from groups 3 to 8, preferably from 4-, 5 - or 6-th group, or of the series of lanthanides and actinides of the Periodic table of elements. Examples of these catalytic compounds, metallocene type with the bulky ligand and catalytic systems are presented, for example, in US patents№№4530914, 4871705, 4937299, 5017714, 5055438, 5096867, 5120867, 5124418, 5198401, 5210352, 5229478, 5264405, 5278264, 5278119, 5304614, 5324800, 5347025, 5350723, 5384299, 5391790, 5391789, 5399636, 5408017, 5491207, 5455366, 5534473, 5539124, 5554775, 5621126, 5684098, 5693730, 5698634, 5710297, 5712354, 5714427, 5714555, 5728641, 5728839, 5753577, 5767209, 5770753 and 5770664, all of which are in full included in this description as a reference, and European publications EP-A 0591756, EP-A 0520732, EP-A 0420436, EP-B1 0485822, EP-B1 0485823, EP-A2 0743324 and EP-B1 0518092 and PCT publications WO 91/04257, WO 92/00333, WO 93/08221, WO 93/08199, WO 94/01471, WO 96/20233, WO 97/15582, WO 97/19959, WO 97/46567, WO 98/01455, WO 98/06759 and WO 98/011144, and all of them to describe a typical catalytic metallocene compounds of the type with the bulky ligand and catalytic systems were fully integrated in the present description as a reference.

In one embodiment of the invention, the catalytic metallocene compound type with the bulky ligand correspond to the formula:

where M denotes a metal atom, which belongs to m is a metal from the ranks of the lanthanides or actinides, moreover, the preferred value of M is a transition metal atom of group 4, and more preferably zirconium, hafnium or titanium; LANDand LINdenote bulky ligands, which include derivateservlet of cyclopentadienyl ligands, substituted derivateservlet of cyclopentadienyl ligands, heterocomplexes or heteroaromatics derivateservlet of cyclopentadienyl ligands, gidrokarbonatnye derivateservlet of cyclopentadienyl ligands or residues, such as Ingenierie ligands, benzydamine ligands, fluorenyl ligands, octahydrophenanthrene ligands, cyclooctatetraene ligands, asenalnoye ligands, barbentane ligands, etc., including their hydrogenated versions. In addition, LANDand LINcan identify ligands of any other structures capable of forming with the M-5. So, for example, LAand LBmay include one or more heteroatoms, in particular nitrogen, silicon, boron, germanium and phosphorus, in combination with the carbon atoms with the formation of a cyclic structure, for example heterocyclization auxiliary ligand. Moreover, each of the LAand LBcan also refer to objaction, aryloxides, imides, carballido, ballidu, porphyrins, phthalocyanines, korinov and other polyazamacrocycles. LAand LBmay designate the bulky ligands are the same or different types, which is associated with M

Each of the LAand LBmay be substituted by a combination of substitute groups R. non-limiting examples of substituting groups R include a hydrogen atom and linear and branched alkyl radicals, cyclic alkyl, alkeline, alkyline and aryl radicals and combinations thereof containing 1-30 carbon atoms and the other substituents, each containing up to 50 non-hydrogen atoms, which can also be substituted. Non-limiting examples of alkyl substituents R cover of methyl, ethyl, through boutelou, pentelow, hexeline, cyclopentyloxy, tsiklogeksilnogo, benzyl and phenyl groups, halogen atoms, etc., including all their isomers, for example tertiary butyl, isopropyl, etc. Other hydrocarbon radicals include formerly, perately, deperately, idproperty, Bromhexine, chloraniline and gidrokarbonatnye metalloorganic radicals including trimethylsilyl, trimethylgermyl, methyldiethylamine and so is Teal)silyl, bromomethylphenyl and so on; and disubstituted boron radicals including, for example, Dimethylol; disubstituted pnictogens radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphinic; chalcogenide radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfinyl and ethylsulfinyl. For the non-hydrogen substituents R include the atoms carbon, silicon, nitrogen, phosphorus, oxygen, tin, germanium, etc., including olefins, such as though not limited to, alafinova-unsaturated substituents including ligands with terminal vinyl, for example but - 3-enyl, 2-vinyl or hexene-1. In addition, at least two groups R, preferably two adjacent groups R are associated with the formation of a ring structure containing 4-30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, boron and combinations thereof. Group R, such as 1-butanol, may also be formed with the metal M is a σ-bond.

With the transition metal can be linked with other ligands, such as leaving group Q. Q can be independently denote monoamine movable ligands, forming a s M a σ-bond. Non-limiting examples of Q include the remains weak bases, such as amines, phosphines, ethers, carboxylates, d is deposits. Other examples of the radicals Q include those substituents at R, which is shown above, including cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene and pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis(N-methylaniline), dimethylamine, dimethylphosphine radicals, etc.

In addition, the catalytic metallocene compound type with the bulky ligand according to the invention are those compounds in which LAand LBlinked bridging group A. These compounds with bridging communication known as bridge catalytic metallocene compound type with the bulky ligand. For non-limiting examples of bridging group a include bridging radicals with at least one atom of group 14, such as, though not limited to, atoms of carbon, oxygen, nitrogen, silicon, germanium and tin, preferably carbon, silicon and germanium, most preferably silicon. Other non-limiting examples of bridging group a include dimethylsilane, dietildisul, medietilsynet, cryptomaterial, bis(trifluoromethyl)-silyl, di-n-Boticelli, siliciclastic, diisopropylzinc, dicyclohexylmethyl, divinycell, cyclohexylaniline, tert-bulilan, diphenylmethylene, ethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene, dimethylethylenediamine, methylenedianiline, methylamine, phenylamine, cyclohexylamine, methylphosphine, phenylphosphine, cyclohexylmethyl etc.

Alternatively the catalytic metallocene compound type with the bulky ligand according to the invention corresponds to the formula:

in which M denotes a transition metal of group 4, 5 or 6, (C5H4-dRd)

denotes unsubstituted or substituted derivationally from bulky cyclopentadienyl ligand bound to M, each R, which may be identical or different, denotes a hydrogen atom or a substituted group containing up to 50 non-hydrogen atoms, substituted or unsubstituted hydrocarbon containing 1-30 carbon atoms, or combinations thereof or two or more carbon atoms are linked with the formation of part of a substituted or unsubstituted ring or ring system containing 4-30 carbon atoms, And a denotes a radical containing one or more atoms, or a combination of atoms of carbon, germanium, silicon, tin, phosphorus and nitrogen linking bridge connection of two rings (C5NC, R'2Si, R'2SiR'2Si, R'2SiR'2C, R'2Ge, R'2SiR'2Ge, R'2GeR'2C, R N, R P, R'2CR'N, R'2CR'P, R'2SiR'N, R'2SiR'P, R'2GeR'N, R'2GeR'P, where R' independently denotes a radical, which is a hydride, a1-C30-hydrocarbon, substituted hydrocarbon, Halocarbon, substituted Halocarbon, gidrokarbonatnyj metalloorganicheskie balance, allocability the metalloid organic residue, disubstituted boron, disubstituted pnicogen, substituted chalcogen or halogen atom; each Q which can be identical or different, denotes a hydride, substituted or unsubstituted linear, cyclic or branched hydrocarbon containing 1-30 carbon atoms, a halogen atom, an alkoxide residue, aryloxides, amide, phosphide or any other univalent anionic ligand or a combination thereof; two groups Q may also be formed alkylidene ligand or cyclometalation hydrocarbon ligand, or other divalent anionic chelating ligand, where g denotes an integer corresponding to the formal oxidation state of M, d denotes an integer selected from 0, 1, 2, 3 and 4, and indicates the degree of substitution, AO type with the bulky ligand are those compounds in which the substituents R bulky ligands LALB, (C5H4-dRdin formulas (I) and (II) is substituted by the same or different number of substituents at each of the bulky ligands.

In a preferred embodiment, the metallocene catalyst of the type with the bulky ligand corresponds to formula (II), where x denotes 1.

Other catalytic metallocene compounds of the type of bulky ligand that can be used according to the invention include bridged metallocene compounds of the type containing one bulky ligand with a 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 and WO 97/15602, in US patents№№5057475, 5096867, 5055438, 5198401, 5227440 and 5264405 and European publications EP-A 0420436, all of which are in full included in this description as a reference. Other metallocene catalysts of the type of bulky ligand that can be used according to the invention include those that are presented in US patents№№5064802, 5145819, 5149819, 5243001, 5239022, 5276208, 5296434, 5321106, 5329031, 5304614, 5677401 and 5723398, in PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144 and European publications EP-A 0578838, EP-A 063859>/P>In another variant implementation of the present invention bridge the catalytic metallocene compound of the type containing one bulky ligand with a heteroatom, which can be used according to the invention correspond to the formula:

in which M represents Ti, Zr or Hf; (C5H5-y-xRxrefers cyclopentadienyls ring or ring system which is substituted by 0-5 replacement groups R, "x" denotes 0, 1, 2, 3, 4 or 5, meaning the degree of substitution, and each replacement group R independently represents a radical selected from the series comprising hydrocarbon WITH1-C20radical, substituted hydrocarbon WITH1-C20radicals in which one or more hydrogen atoms substituted by a halogen atom, gidrokarbonatnye metallogenia1-C20radicals, in which the atom of the metalloid is selected from group 14 of the Periodic table of elements, or halogen radicals or (C5H5-in-xRxrefers cyclopentadienyls ring in which two adjacent groups R are related to education4-C20-rings, resulting in a gain saturated or unsaturated polycyclic cyclopentadienyls ligand, such ka is Ohm ligand, in which J denotes an element with a coordination number of three from group 15 or an element with a coordination number of two from group 16 of the Periodic table of elements, preferably nitrogen, phosphorus, oxygen or sulfur, preferably nitrogen, and each R' independently represents a radical selected from the series comprising hydrocarbon WITH1-C20radicals in which one or more hydrogen atoms substituted by a halogen atom, y denotes 0 or 1, a "z" denotes the coordination number of the element J;

each Q independently represents any univalent anionic ligand such as halogen atom, a residue of a hydride, substituted and unsubstituted C1-C30the hydrocarbon residue alkoxide, aryloxides, amide or phosphide, provided that two Q can denote alkyliden, cyclometalation hydrocarbon or any other divalent anionic chelating ligand; and n may denote 0, 1 or 2;

And denotes a covalent bridging group containing an element of group 15 or 14, such as, though not limited to, dialkyl-, alkylaryl-, diarylquinoline and germanium radical, alkyl - and arylphosphine and amine radicals and the hydrocarbon radical such as methylene, ethylene, etc.;

According to another variant of the catalytic metallocene compound type with the bulky ligand is a complex of a transition metal, a substituted or unsubstituted PI-bonded ligand, and one or more heteroallyl residues, such as those presented in US patents No. 5527752 and 5747406 and in EP-B1 0735057, all of which are in full included in this description as a reference. The preferred catalytic metallocene compound type with the bulky ligand, monotsiklopentadienil catalytic compound can be represented by one of the following formulas:

in which M denotes a transition metal atom of group 4, 5 or 6, preferably titanium, zirconium or hafnium, most preferably zirconium or hafnium, L denotes a substituted or unsubstituted PI-associated ligand coordinated to M, the preferred value of L is cycloalkenyl bulky ligand, such as cyclopentadienyls, intenally or fluoroaniline bulky ligand, optional is achene each Q is independently selected from the series including-O-, -NR-, -CR2- and-S-, preferably an oxygen atom; Y denotes either C or S, preferably a carbon atom; 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, -PR3and-N, the preferred value of Z is chosen from a range including-OR, -CR3and-NR2; n denotes 1 or 2, preferably 1; And denotes a univalent anionic group when n represents 2, or a denotes a divalent anionic group when n denotes 1, the preferred value of a is a carbamate, carboxylate, or other heteroallyl residue represented by the combination of Q, Y and Z; each R independently denotes a group containing carbon, silicon, nitrogen, oxygen and/or phosphorus where one or more R groups can be linked with the Deputy L, and the preferred value of R is a hydrocarbon group containing 1-20 carbon atoms, most preferably alkyl, cycloalkyl or aryl group, and one or more may be associated with Deputy L; T denotes a bridging group, vibe substituted carbon or the heteroatom (heteroatoms), germanium, silicon and alkylphosphine; m is 2 to 7, preferably 2 to 6, most preferably 2 or 3.

In formulas (IV) and (V) auxiliary Deputy, formed by the Q, Y and Z, is a single shot polydentate ligand due to its high polarizability, providing electronic effect similar to the effect of cyclopentadienyls ligand. In the most preferred versions of the present invention use disubstituted carbamates and carboxylates. Non-limiting examples of these catalytic compounds, metallocene type with the bulky ligand include indenyltitanium(diethylcarbamyl), indenyltitanium(trimetilatsetat), indenyltitanium(p-toluate), indenyltitanium(benzoate), (1-methylindenyl) zirconias (trimetilatsetat), (2 - methylindenyl) zirconium-Tris (diethylcarbamyl), (methylcyclopentadienyl) zirconias (trimetilatsetat), cyclopentadienylzirconium (trimetilatsetat), tetrahydrocortisone-Tris (trimetilatsetat) and (pentamethylcyclopentadienyl) zirconias (benzoate). Preferred examples are indenyltitanium (diethylcarbamyl), indenyltitanium (trimetilatsetat) and (methylcyclopentadienyl) zirconias (the first type with the bulky ligand represent a nitrogen-containing heterocyclic ligand complexes, also known as catalysts with transition metal-based containing bidentate ligands pyridine and quinoline residues, such as those presented in the applications WO 96/33202, WO 99/01481 and WO 98/42664 and US patent No. 5637660, and they are all included in the present description as a reference.

In one embodiment, covered by the scope of the present invention, the catalytic metallocene compound type with the bulky ligand which complexes Ni2+and Pd2+provided in the articles Johnson and others, "New Pd(II) - and Ni(II)- Based Catalysts for Polymerization of Ethylene and-Olifins", J. Am.Chem.Soc. 1995, 117, 6414-6415 and Johnson and others, "Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium (II) Catalysts", J. Am.Chem.Soc. 1996, 118, 267-268, and in the application WO 96/23010, published August 1, 1996 (and they are all included in the present description as a reference), can be used in combination with a carboxylate metal salt in the implementation of the method according to the invention. These complexes can be either addition products dialkylamide ester or alkylated reaction products described dihalogenide complexes that can be activated by cationic state with socialization conventional type or activators of the present invention, described the connection with ligands on diimino the basis for the metals of groups 8-10, 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), and they are all included in the present description as a reference.

Other metallocene catalysts of the type with the bulky ligand are imagecomplete metals of groups 5 and b, presented in EP-A2 0816384 and in US patent No. 5851945, which are included in the present description as a reference. In addition, the metallocene catalysts of the type with the bulky ligand include bridge bizarrement compounds of elements of groups 4, represented in the work of D. H. McConville and others in Organometallics 1195, 14, 5478-5480, which is incorporated into this description by reference. Other metallocene catalysts of the type with the bulky ligand represented as bis(hydroxyaromatic nitrogen ligands) in US patent No. 5852146, which is included in the present description by reference. Another metallocene catalysts of the type containing one or more atoms of elements in group 15 include those presented in the application WO 98/46651, which is incorporated into this description by reference. However, other catalysts of the metallocene type with the bulky ligand include those polycyclic metallocene catalysts of the type voluminous is 2">

In some embodiments, provides for the possibility of an asymmetric substitution of the above-described catalytic metallocene compounds of the type with the bulky ligand according to the invention in the sense of additional substituents or types of substituents and/or imbalance in a sense different numbers of additional substituents at bulky ligands or ligands themselves.

In one embodiment, the list of metallocene catalysts of the type with the bulky ligand according to the invention provides for the inclusion of their structural, optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof. In another embodiment, the metallocene compounds of the type with the bulky ligand according to the invention can be chiral and/or bridge catalytic metallocene compounds of the type with the bulky ligand.

Activator and methods of activation of the catalytic metallocene compounds of the type with the bulky ligand

The above catalytic metallocene compound type with the bulky ligand according to the invention, generally activate different ways to get the catalytic compounds with a free coordination site, which ensure the awci and the accompanying claims, the term "activator" is defined as referring to any compound, component, or method, which provides the ability to activate any of the above catalytic metallocene compound type with the bulky ligand according to the invention. Non-limiting examples of activators include Lewis acid, recoordination ionic activators, ionizing activators and any other connections, including grounds Lewis, aluminiumgie, socializaton conventional type (above in the present description), and combinations thereof that can convert a neutral catalytic metallocene compound type with the bulky ligand in connection with the catalytically active metallocene cation type with the bulky ligand. The scope of the present invention covers the use of alumoxane or modified alumoxane as activator and/or also use ionizing activators, neutral or ionic, such as Tris(n-butyl)ammoniates(pentafluorophenyl)boron, tripartitions metallogeny predecessor or tripartition metallogeny predecessor, connection polyhalomethanes heteroborane anions (see WO 98/43A 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 education as catalytic metallocene cation type with the bulky ligand, and coordinating anion, as described in applications EP-A 0426637 and EP-A 0573403 and in US patent No. 5387568, and they are all included in the present description as a reference.

There are many ways to get alumoxane and modified alumoxanes, examples of which are presented in US patents№№4665208, 4952540, 5091352, 5206199, 5204419, 4874734, 4924018, 4908463, 4968827, 5308815, 5329032, 5248801, 5235081, 5157137, 5103031, 5391793, 5391529, 5693838, 5731253, 5731451 and 5744656 in European publications EP-A 0561476, EP-B1 0279586 and EP-A 0594218 and in PCT publication WO 94/10180, all of which are in full included in this description as a reference.

Ionizing compounds can include an active proton, or some other cation associated, but a disorderly or only subcoordinators with the remaining ion of the ionizing compound. Such compounds, etc., presented in European publications EP-A 0570982, EP-A 0520732, EP-A 0495375, EP-A 0500944, EP-A 0277003 and EP-A 0277004, in US patents№№5153157, 5198401, 5066741. 5206197, 5241025. 5384299 and 55021 the present description as a reference.

Other activators include those compounds which are represented in PCT publication WO 98/07515, such as Tris(2,2',2"-nonaboriginal)-peraluminous, and this publication in full included in the present description by reference. The invention also provides the use of combinations of activators, such as combinations of alumoxanes with ionizing activators (see, in particular, the publication EP-B1 0573120, PCT WO 94/07928 and WO 95/14044 and patents US 5153157 and 5453410, all of which are in full included in this description as references). In the application WO 98/09996 included in the present description by reference, describes the catalytic activation of the metallocene compounds of the type with the bulky ligand perchlorate, periodate and Iodate, including their hydrates. In applications WO 98/30602 and WO 98/30603, which are included in the present description as reference, describes the use of lithium (2,2'- biphenyldicarboxylic)·THF as catalytic activator for the metallocene compounds of the type with the bulky ligand. In the application WO 99/18135 included in the present description by reference, describes the use of organic boron-aluminum activators. In the application EP-B1 0781299 described the use of sicilieweg salt in combination with coordinationin owls is m ligand or predecessor in connection with the metallocene cation type with the bulky ligand, able to provide the polymerization of olefins, is also provided the use of such activation methods, as using radiation (see application EP-B1 0615981 included in the present description by reference), electrochemical oxidation, etc., Other activators and activation methods catalytic metallocene compound type with the bulky ligand represented, for example, in US patents No. 5849852, 5859653 and 5869723 and in PCT publication WO 98/32775, which are included in the present description as a reference.

Mixed catalysts

The scope of the present invention covers also the possibility of combining the above-described catalytic metallocene compounds of the type with the bulky ligand with one or more catalytic compounds corresponding to formula (I), (II), (III), (IV) and (V), in combination with one or more activators or by the methods described above activation.

According to the invention provided hereinafter, the possibility of combining other catalysts from catalytic metallocene compounds of the type with the bulky ligand according to the invention (see, for example, US patents№№4937299, 4935474, 5281679, 5359015, 5470811 and 5719241, all of which are in full included in this description of kachestva metallocene type with the bulky ligand or catalyst systems may be 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 patents№№4159965, 4325837, 4701432, 5124418, 5077255, 5183867, 5391660, 5395810, 5691264, 5723399 and 5767031 and in PCT publications WO 96/23010 from August 1, 1996, all of which are in full included in this description as a reference.

In addition, the possibility of combining two or more catalysts conventional type with transition metal with one or more socialization conventional type. Non-limiting examples of mixed catalysts of conventional type with a transition metal, for example, in US patents№№4154701, 4210559, 4263422, 4672096, 4918038, 5198400, 5237025, 5408015 and 5420090, all of which are included in the present description as a reference.

The method of applying to the media

The above catalytic metallocene compound type with the bulky ligand and catalytic systems and catalytic compounds with transition metal and the catalytic system of the usual type may be combined with one or more substrate materials or carriers using one of the methods of application are well known in the art or as set forth below. In a preferred variant of the method is the most preferred embodiment, the catalytic metallocene compound type with the bulky ligand or catalyst system is supported on a carrier form, for example deposited on a substrate or carrier, in contact with or embedded in it, adsorbed or absorbed.

The terms "substrate" and "carrier" are used interchangeably, they are applicable to any porous or non-porous material medium, it is preferable for the porous material of the carrier, such as talc, inorganic oxides and inorganic chlorides. Other media include resinous materials of media, such as polystyrene, functionalized or crosslinked organic media, such as polystyrene-divinylbenzene polyolefin and the polymer products, any other organic or inorganic materials, media, etc. 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 media include magnesium oxide, titanium dioxide, zirconium dioxide, montmorillonite, etc., Can be used as combinations of these materials carriers, such as kranidioti/chrome and kranidioti/titanpoker.

due surface in the range from about 10 to about 700 m2/g and a pore volume in the range of from about 0.1 to about 4.0 cm3/g and an average particle size in the range of from about 10 to about 500 microns. In a more preferred embodiment, the specific surface area of the carrier is in the range from about 50 to about 500 m2/g and the pore volume is in the range from about 0.5 to about 3.5 cm3/g and the average particle size is from about 20 to about 200 microns. In the most preferred embodiment, the specific surface area of the carrier is in the range from about 100 to about 400 m2/g and a pore volume from about 0.8 to about 3.0 cm3/g and the average particle size is in the range from about 20 to about 100 microns. The average pore size of the carrier according to the invention generally ranges from about 10 to about 1000 , preferably from about 50 to about 500 , and most preferably from about 75 to about 350 .

Examples of application to the media metallocene catalytic systems of the type with the bulky ligand according to the invention are, in particular, in US patents№№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, bee PCT WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297, all of which are in full included in this description as a reference.

Examples of application to the carrier of the catalytic systems of the conventional type according to the invention are, in particular, in US patents№№4894424, 4376062, 4395359, 4379759, 4405495, 4540758 and 5096869, all of which are included in the present description as a reference.

The possibility of applying catalyst metallocene compounds of the type with the bulky ligand according to the invention in conjunction with the activator on the same or separate carriers or activator can be used in not supported on a carrier form, or may be supported on a carrier other than the carrier that caused the catalytic metallocene compound type with the bulky ligand according to the invention, or can use any combination of these options.

In the art there are various other methods of applying a polymerization catalyst compound or catalyst system according to the invention. So, for example, catalytic metallocene compound type with the bulky ligand according to the invention can include associated with the polymer ligand, as described in US patents No. 5473202 and 5770755 that gender is Emistim ligand according to the invention can be dried by spray as described in US patent No. 5648310, which fully included in the present description by reference; the media used in combination with the catalyst system of the metallocene type with the bulky ligand according to the invention, functionalitywith as described in European publication EP-A 0802203, which fully included in the present description by reference; or at least one Deputy or a leaving group chosen as described in US patent No. 5688880, which fully included in the present description by reference.

In a preferred embodiment, the invention features supported on a carrier metallocene catalyst system of the type with the bulky ligand comprising a surface modifier, which is used in the preparation of the catalytic system on the medium as set forth in PCT publication WO 96/11960, which fully included in the present description by reference.

The preferred method of preparing a metallocene catalytic system of the type with the bulky ligand on the media according to the invention described below, it can be found in the patent applications US serial number 265533 filed June 24, 1994, and 265532, filed 24 July the volume included in the present description as a reference. In this preferred method, the catalytic metallocene compound type with the bulky ligand suspended in a 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 catalytic metallocene compounds of the type with the bulky ligand and/or the activator according to the invention, the solution or etc In the most preferred embodiment, as the liquid used cycloaliphatic or aromatic hydrocarbon, preferably toluene. Solutions of catalytic metallocene compound type with the bulky ligand and activator are mixed and added to a porous carrier or a porous carrier added to these solutions so that the total amount of catalytic solution of the metallocene compound type with the bulky ligand and activator solution or the solution of the catalytic metallocene compound type with the bulky ligand and activator was less than five times the volume of pores of a porous support, more preferably less than four times, and even more preferably less than three times alhammadi determine the total pore volume of the porous media 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 (Academic Press, 1968) (see specifically with. 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 catalytic metallocene compounds of the type with the bulky ligand is in the range of 0.3:12000:1, preferably 20:1-800:1, and most preferably 50:1-500:1. When the activator is the ionizing activator such as activators based on anionic Tetra-KIS(pentafluorophenyl)boron, the preferred molar ratio between the metal of the activator component and the metal component of the catalyst is in the range of 0,3:13:1.

One variant of execution of the invention before the main polymerization process in the presence of a metallocene catalyst system of the type with the bulky ligand and/or catalysts of conventional type with a transition metal according to the invention will terpolymeric olefin (a-olefins) is roelen, or combinations thereof. The process of terpolymerization can be periodic or continuous in gas, solution or slurry phase, including the creation of high blood pressure. Terpolymerization can be any olefin monomer and/or combinations thereof in the presence of any of regulating the molecular weight of the agent, such as hydrogen. Examples of terpolymerization can be found in US patents№№4748221, 4789359, 4923833, 4921825, 5283278 and 5705578, in European publication EP-0279863 and PCT publication WO 97/44371, all of which are in full included in this description as a reference. Considering the purpose of the present description and attached claims, as a catalytic system for terpolymerization used catalytic system on the media.

Carboxylate metal salt

Carboxylate metal salts in the art well known as additives for use in combination with polyolefins, for example, as a substance to improve the processing properties of the film. Postreactor technological additives of these types are widely used as emulsifiers, antistatic agents and anti-clouding, stabilizers, substances that promote proobraz the tion and caking, etc., Therefore, the fact that these postreactor additives or auxiliary substances could be used in combination with a polymerization catalyst to increase the efficiency of the polymerization process, was really unexpected.

Considering the purpose of the present description and attached claims, the term "carboxylate metal salt" is used to refer to any salt formed by the residue of mono-, di - or tricarboxylic acid and the metal ingredient of the Periodic table of elements. Non-limiting examples include salts of saturated, unsaturated, aliphatic, aromatic and saturated cyclic carboxylic acids, the preferred carboxylate ligand containing 2-24 carbon atoms, such as acetates, propionate, butyrate, valerate, pivalate, caproate, isobutylacetate, tert-butyl, caprylate, heptanoate, pelargonate, undecanoate, oleates, octoate, palmitate, myristate, Margarita, stearates, arahata and arcosanti. Non-limiting examples of the metal ingredient of the Periodic table of elements include those selected from the group Al, Mg, Ca, Sr, Sn, Ti, V, BA, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li, and Na.

Included in the composition Carbo which means the metal atom of group III of the Periodic table;

Q denotes hydroxyl; R is a hydrocarbon radical containing 2-100 carbon atoms, preferably 4-50 carbon atoms; x represents an integer 1 or 2; y represents an integer of 1 or 2, and the sum of x and y is equal to the valence of the metal.

Non-limiting examples of values of R in the above formula include hydrocarbon radicals containing 2-100 carbon atoms, which include alkyl, aryl, aromatic, aliphatic, cyclic, saturated and unsaturated hydrocarbon radicals. In one embodiment of the invention, R is a hydrocarbon radical containing 8 or more carbon atoms, preferably 12 or more carbon atoms, and more preferably 17 or more carbon atoms. In another embodiment, R is a hydrocarbon radical, including 17-90 carbon atoms, preferably 17-72, and most preferably 17-54 carbon atoms.

However, Q may mean alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkyl, alkylaryl, alkylsilane, arrelano, alkylamino, arylamino, alkylphosphine, alkoxygroup containing 1-30 carbon atoms. Such carbohydrate oradatabase group may be the as a halide, sulfate and phosphate.

One option preferred carboxylate salts of the metals are aluminum carboxylates such as aluminimun-, di - and tristearate, aluminiumcoated, oleates and-cyclohexanebutyrate. However, in the preferred embodiment, the carboxylate metal salt is a [CH3(CH2)16COO]3Al, aluminiumtitanat (preferably with a melting point 115S), [CH3(CH2)16COO]2-Al-OH, elminister (preferably with a melting point C) or CH3(CH2)16-l(OH)2aliminiumnation (preferably with a melting point 155).

Non-limiting examples of technically available carboxylate metal salts include Witco Aluminum Stearate #18, Witco Aluminum Stearate # 22, Witco Aluminum Stearate # 132 and Witco Aluminum Stearate EA Food Grade, all of which are available on the company Witco Corporation, Memphis, PCs Tennessee.

One of the options melting point carboxylate metal salt is from about 30 to about S, more preferably from about 37 to about 220C, even more preferably from about 50 to about 200C, and most preferably from about 100 to about 200C. the tour whose melting point is in the range from about 135 to about S.

According to another preferred variant, the melting temperature of carboxylate metal salt exceeds the polymerization temperature in the reactor.

Other examples of carboxylate metal salts include titanium stearates, tin stearates, stearates of calcium, zinc stearates, stearates boron and stearates of strontium.

Other examples of carboxylate metal salts include titanium stearates, tin stearates, stearates of calcium, zinc stearates, stearates boron and stearates of strontium.

One of the options carboxylate metal salt can be used in combination with antistatic agents such as fatty amines, such as zinc additive Kemamine AS 990/2, a mixture of polyoxyethylene stearylamine with zinc stearate, and Kemamine AS 990/3, a mixture of polyoxyethylene stearylamine with zinc stearate and octadecyl-3,5-decret-butyl-4-hydroxyhydrocinnamate. Both of these mixes available on the company Witco Corporation, Memphis, PCs Tennessee.

The method of preparation of the catalytic composition

The method of preparation of the catalytic compositions typically involves combining, contacting, blending and/or mixing the catalyst system or polymerization catalyst with a carboxylate metal salt.

In another embodiment, the stage of the method according to the invention include the preparation of a polymerization catalyst, preferably the preparation of the polymerization catalyst on the carrier, and contacting the polymerization catalyst with at least one carboxylate metal salt. In a preferred variant of the method, the polymerization catalyst includes a catalyst compound, an activator or acetalization and the media, preferably the polymerization catalyst is a metallocene catalyst of the type with the bulky ligand on the media.

Specialist in the art it is known that depending on the catalytic system and the carboxylate metal salt to prevent, for example, loss of activity of the catalytic system would require certain conditions of temperature and pressure.

In one embodiment of the method of the political system on the media, most preferably the catalyst system of the metallocene type with the bulky ligand on the media, at normal temperature and pressure. The preferred temperature probe for combining a polymerization catalyst and a carboxylate metal salt is in the range from 0 to about 100C, preferably from 15 to about 75S, most preferably at about normal temperature and pressure.

In a preferred embodiment, the contacting the polymerization catalyst with a carboxylate metal salt is carried out in an atmosphere of inert gas, such as nitrogen. However, it is possible to perform phase alignment polymerization catalyst with a carboxylate salt of the metal in the environment of the olefin (olefin), solvents, hydrogen, etc.

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

According to one variant of the method according to the invention, the polymerization catalyst and the carboxylate metal salt combine in a fluid environment, which can be, for example, mineral oil, toluene, hexane, isobutane IP polymerization catalyst, which is cooked in a liquid, preferably in the form of a suspension, or combine with practically dry or dried polymerization catalyst which is introduced into the liquid and suspended.

In one embodiment, the time of contact carboxylate metal salt with a polymerization catalyst can be varied depending on one or more conditions of temperature and pressure, type of mixing apparatus, the quantities of components that must be combined, and even from the mechanism the combination of a polymerization catalyst/carboxylate salt of the metal in the reactor.

In a preferred embodiment, the polymerization catalyst, preferably a catalytic metallocene compound type with the bulky ligand and the carrier is introduced into contact with the carboxylate metal salt for a period of time from about seconds to about 24 hours, preferably from about 1 minute to about 12 hours, more preferably from about 10 minutes to about 10 hours, and most preferably from about 30 minutes to about 8 hours

In one embodiment, the ratio between the weight of the carboxylate metal salt and the weight of the transition metal catalyst compounds nahoditsya in the range of from about 2 to about 50, and most preferably in the range of from 4 to about 20. In one embodiment, the ratio between the weight of the carboxylate metal salt and the weight of the transition metal catalyst compound is in the range from about 2 to about 20, more preferably in the range of from about 2 to about 12, and most preferably in the range of from 4 to about 10.

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

In one embodiment, in which, according to the method according to the invention receive polim is based metal salt, calculated on the total weight of the polymerization catalyst exceeds 1 wt.%. In yet another variant, in which, according to the method according to the invention receive the polymer product, the density of which sostavlat less than 0.910 g/cm3the total mass percentage of carboxylate metal salt, calculated on the total weight of the polymerization catalyst exceeds 3 wt.%. If the polymerization catalyst comprises a carrier, the total weight of the polymerization catalyst include the mass media.

I believe that the higher the metal content of the activator, for example, the total aluminium content or the content of free aluminum (content aluminiumgie in alumoxane), a polymerization catalyst, the more you want carboxylate metal salt. Manipulation of quantities or content components of a polymerization catalyst, i.e., free of aluminum, can serve as a means of controlling the content of the carboxylate metal salt.

Methods of mixing and equipment provided for use in the method according to the invention, are well known. The method of mixing may include the use of any mechanical means of mixing, such as shaking, stirring, surface finishing process and roll it out. Other methods provided include the use of p the circulating gases. Non-limiting examples of mixing equipment for combining in the most preferred embodiment, the solid polymerization catalyst and solid carboxylate metal salt include a ribbon mixer, a static mixer, double-cone mixer, a tumbling drum, paribanou rolling mill, apparatus for breaking emulsions, a mixer, a fluidized bed mixer spiral mixer and mixer with a tapered screw.

In one embodiment of the method according to the invention the catalyst is a conventional-type transition metal on a carrier, preferably supported on a carrier catalyst metallocene type with the bulky ligand, galuut together with the carboxylate metal salt for a period of time sufficient for homogeneous mixing and/or practical introduction a substantial part of the catalyst on the carrier in contact with this carboxylate metal salt.

In a preferred embodiment, a catalytic system according to the invention is applied to the carrier and deposited on the carrier of the catalytic system in the preferred embodiment, is an almost dried, pre-molded, gain preshaped catalytic system on the media enter in contact with at least one carboxylate metal salt. Carboxylate salt of the metal may be in solution, suspension or in dry condition, the preferred carboxylate salt of the metal is almost dry or dried state. In the most preferred embodiment, the carboxylate metal salt introduced into contact with the catalytic system on the carrier, preferably supported on a carrier of the catalyst system of the metallocene type with the bulky ligand, in a drum mixer in a nitrogen atmosphere, and the most preferred mixer is a tumbling drum mixer, or in the process of mixing in the fluidized bed, in which the polymerization catalyst and the carboxylate metal salt are in the solid state, i.e., they both are practically dry state or in a dried state.

In one embodiment of the method according to the invention for the preparation of catalytic compounds on the carrier of a catalytic compound of a transition metal of conventional type, preferably a catalytic metallocene compound type with the bulky ligand, enter in contact with the media. In this embodiment of the method of the activator or acetalization for catalytic compound is administered in a specific embodiment, the invention before mixing separately supported on a carrier of catalyst and activator or socializaton provided in any order subsequent mixture of carboxylate metal salt with a catalytic compound on the carrier or the activator or acetalization on the media, separately mixed, simultaneously mixed, or mixed with only one of the catalysts on the media, or preferably supported on a carrier activator.

Due to a combination of a polymerization catalyst/carboxylate metal salt according to the invention may be a need to improve the flow into the reactor as a whole. Despite the fact that the flow of the stream of catalyst is not as effective as the catalyst without the carboxylate metal salt, the flowability of the combination catalyst/carboxylate according to the invention does not create problems. If the incoming stream of catalyst needs to be improved in the art are well aware of the use of hopper vibrators, brush mechanical feeders for catalyst feeders blowing pressure, etc.

In another embodiment, the polymerization catalyst/carboxylate metal salt can be inserted to contact with liquid, such as mineral oil, and used in the polymerization process in suspended state. In this particular preferred embodiment, the polymerization catalyst is a curing catalyst for the media.

In some the of such processes is more difficult. It was found that the application of a combination of a polymerization catalyst and a carboxylate metal salt according to the invention allows efficient use of materials-media with particles of smaller sizes, in particular silicon dioxide, average particle size which ranges from about 10 to 80 μm. Kremmidiotis materials with such a particle size is available on the company Crosfield Limited, Warrington, England, in particular the product of the Crosfield ES-70, the average particle size of which is 35-40 microns. Not based on any theory, traditionally believed that the application of media in the form of particles of smaller average size produce more stuff, and get the catalyst on the carrier responsible for the formation of increased amounts of sediments. I also believe that the application of the carboxylate metal salt with a polymerization catalyst provides improved growth of the particles during the polymerization. The consequence of this improved morphology of the particles is believed to be fewer details and less tendency to form deposits. Thus, the use of carboxylate metal salt enables the use of smaller carrier material.

In one embodiment, for izobretatelnee metal salt in the reactor. One of the options polymerization catalyst used is not supported on a carrier form, preferably in the form of a liquid, such as described in US patents No. 5317036 and 5693727 and European publications EP-A 0593083, all of which are included in the present description as a reference. The polymerization catalyst in liquid form can be introduced into the reactor together with a carboxylate salt of the metal with the application of methods of injection presented in PCT publication WO 97/46599, which fully included in the present description by reference.

When using a combination of carboxylate metal salt and is not supported on a carrier metallocene catalytic system of the type with a bulky ligand, the molar ratio between the metal of the activator component to the metal of the catalytic metallocene compound type with the bulky ligand is in the range of 0.3:1-10000:1, preferably 100:1-5000:1, and most preferably 500:1-2000:1.

The polymerization process

Catalysts and catalytic systems according to the invention, described above, are acceptable for use in any method of polymerization. Polymerization processes include polymerization using solution gas FFL in the gas phase or slurry phase of one or more 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 in solution, suspension or gas phase of one or more olefinic monomers containing 2-30 carbon atoms, preferably 2-12 carbon atoms, and more preferably 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 ethylene-unsaturated monomers, diolefin containing 4-18 carbon atoms, paired and unpaired diene, polyene, vinyl monomers and cyclic olefins. Non-limiting examples of monomers that may be used according to the invention may include norbornene, norbornadiene, isobutylene, vinylbenzoate, styrene, alkyl substituted styrene, ethylidenenorbornene, isoprene, Dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the method according to the invention receive copilului a at least one alpha-olefin, containing 4-15 carbon atoms, preferably 4-12 carbon atoms, and most preferably 4-8 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 process, in particular for gas-phase or slurry to the polymerization of propylene, either individually or together with one or more other monomers, including ethylene and other olefins containing 4 to 12 carbon atoms. Polypropylene polymers may be produced using, in particular of bridged metallocene catalysts of the type with a bulky ligand, as described in US patents No. 5296434 and 5278264, and they are both included in the present description as a reference.

In the process of gas-phase polymerization, as a rule, apply a continuous cycle, in one part of the reactor system in which 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 assign the EBM process of obtaining polymers with fluidized bed through a fluidized bed in the presence of catalyst under reaction conditions continuously circulates the gaseous stream, 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 patents№№4543399, 4588790, 5028670, 5317036, 5352749, 5405922, 5436304, 5453471, 5462999, 5616661 and 5668228, all of which are in full included in this description as a reference).

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

The temperature in the reactor during the gas-phase process may vary from about 30 to about 120C, preferably from about 60 to about 115S, more preferably in the range of from about 70 to about 110S, and most preferably in the range of from about 70 to about S.

Other gas-phase processes, for which it is intended the method according to the present izaberete is-And 0802202, EP-A2 0891990 and EP-0634421, all of which are in full included in this description as a reference.

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) to about 200,000 lbs/HR (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/h), however, even more preferably more than 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 greater than 100,000 lbs/HR (45500 kg/h).

During the process of suspension polymerization usually create a pressure in the range of from about 1 to about 50 at and even greater and temperatures in the interval from 0 to about 120C. 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 add and hydrogen along with catalyst. The suspension comprising the diluent, from relegence return to the reactor. As the liquid diluent in the polymerization medium, as a rule, use alkane containing 3-7 carbon atoms. 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 patent No. 3248179, which fully included in the present description by reference. Other methods of suspension polymerization include those carried out with the use of a reactor with circulation, and methods using multiple reactors mixing hosted posledovatelno, parallel or a combination of these configurations. Non-limiting examples of suspension methods include methods with reactors repocopy carried out in reactors continuous circulation or with a mixer. Other examples of the suspension of the methods presented in US patent No. 4613484, which fully included in the present description by reference.

In one embodiment, the reactor used in the suspension method according to the invention and the method according to the invention provide the possibility of obtaining more than 2000 lbs of polymer per hour (907 kg/HR), 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) to about 100,000 lbs/HR (45500 kg/h).

Examples of methods implemented in the solution presented in US patents No. 4271060, 5001205, 5236998 and 5589555, which are not fully included in the present description as a reference.

In a 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 of the type with the bulky ligand in the absence or near absence of any cleansing supplements, such as triethylaluminum, trimethylaluminum, triisobutylaluminum, Proc. of the PCT WO 96/08520 and US patents No. 5712352 and 5763543, which are not fully included in the present description as a reference. However, it was found that the polymerization process using a combination of the catalytic system/carboxylate metal salt according to the invention can be performed with a small amount of cleansing supplements weakened the influence (or not) on the efficiency of the process and performance of the catalyst. Thus, according to one embodiment of the invention proposes a method of polymerization of olefin (olefin) in a reactor in the presence of a metallocene catalyst system of the type with a bulky ligand, a carboxylate metal salt and cleansing supplements.

In one embodiment, using a polymerization catalyst and/or catalyst composition under polymerization catalyst and the carboxylate metal salt performance exceeds 1500 grams of polymer per gram of catalyst, preferably greater than 2000 grams of polymer per gram of catalyst, more preferably greater than 2500 grams of polymer per gram of catalyst and most preferably greater than 3000 grams of polymer per gram of catalyst.

In another embodiment, using a polymerization catalyst and/or catalytic composizione per gram of catalyst, preferably greater than 3000 grams of polymer per gram of catalyst, more preferably greater than 4000 grams of polymer per gram of catalyst and most preferably greater than 5000 g polymer per gram of catalyst.

In one embodiment, in the case of a polymerization catalyst and/or catalytic composition constant copolymerization is usually less than 2, usually less than 1. For constant copolymerization take the value of the molar ratio between co monomer and a monomer entering the reactor, as determined, for example, the gas composition in the gas-phase process, divided by the value of the molar ratio between the links of the co monomer and monomer in the resulting polymer product. In a preferred embodiment, the constant copolymerization is less than 0.6, more preferably less than 0.4, and most preferably less than 0.3. In the most preferred embodiment, the monomer is ethylene and the co monomer is an olefin containing 3 or more carbon atoms, more preferably an alpha-olefin containing 4 or more carbon atoms, and most preferably the alpha-olefin selected from the group comprising butene-1,4-methylpentene-1, penten-1, hexene-1 and octene-1.

In another dimerization the catalyst, preferably, when the first and second polymerization catalysts are catalytic metallocene compounds of the type with a bulky ligand, preferably when the second curing 'the catalyst are bridging the catalytic metallocene compound type with the bulky ligand, it would be preferable in this transition the use of a catalytic composition carboxylate metal salt in combination with the bridged metallocene catalyst of the type with the bulky ligand.

During the beginning of the polymerization process, particularly a gas phase process high tendency to have problems with the effectiveness of the process. For this reason, to reduce or eliminate emerging at the beginning of the problem the present invention provides the use of a mixture of a polymerization catalyst and a carboxylate metal salt. Furthermore, after the exit of the reactor in a stable mode, there is also the possibility of transition to the same or a different polymerization catalyst without carboxylate metal salt.

In another embodiment, during the process of polymerization, which is interrupted or soon will be interrupted, and can bialla. This switching from one polymerization catalyst to another provided when problems arise with efficiency. Indications of problems with performance in the art are well known. Some of them in gas-phase process include temperature variations in the reactor, unexpected changes in pressure, excessive generation of static electricity or extremely high bursts of static electricity, the formation of lumps, deposits etc. In one of the options you can add directly into the reactor carboxylate metal salt, in particular if you experience problems with efficiency.

It was found that using a polymerization catalyst in combination with a carboxylate metal salt according to the invention, it is easier to achieve a fractional melt index and high density polymers. In one embodiment of the invention proposes a method of polymerization of olefin (olefin) in a reactor in the presence of a polymerization catalyst in combination with a carboxylate metal salt to obtain a polymer product, the melt index is less than about 1 DG/min, and a density higher than 0.9 and a density above 0,925 g/cm3. Preferred polymerization catalyst is a metallocene catalyst of the type with a bulky ligand, a more preferred method is the gas-phase method, and a polymerization catalyst comprises a carrier.

It is assumed that the use of a combination of a polymerization catalyst/carboxylate metal salt according to the invention would ease the transition to the one obtained with more significant difficulties polymers. Thus, one of the options object of the invention is a method of polymerization of olefin (olefin) in the presence of a first catalyst composition in a stationary mode, preferably under conditions of gas-phase process, with receipt of the first polymer product. This first polymer product has a density of more than 0.87 g/cm3preferably more than to 0.900 g/cm3more preferably more than 0.910 g/cm3and a melt index in the range of from 1 to about 200 DG/min, preferably in the range from greater than 1 to about 100 DG/min, more preferably in the range from greater than 1 to about 50 DG/min, most preferably in the range from greater than 1 to about 20 DG/min, This method further includes when letestu over 0,920 g/cm3preferably more than 0,925 g/cm3and a melt index less than 1 DG/min, preferably less than 0.75 DG/min, the second catalytic composition comprises in combination a conventional type catalyst with a transition metal and/or metallocene catalyst of the type with the bulky ligand and the carboxylate metal salt. The volume of this particular option also covers the transition from the first polymer product, the value of I21/I2(described below) is less than 25, the second polymeric product, the value of I21/I2more than 25, preferably greater than 30, more preferably greater than 35.

In yet another embodiment, the method according to the invention includes alternating first catalytic composition which is a mixture of the first polymerization catalyst/carboxylate metal salt and a catalytic composition of the second polymerization catalyst without carboxylate metal salt to improve the overall efficiency of the process. In another embodiment, these first and second catalytic composition described above can be used simultaneously, for example, in the form of a mixture or separate injection into the reactor. In any of these options first and second pole

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, low density polyethylene, polypropylene and polypropylene copolymers.

Polymers, typically ethylene polymers on the basis of, have a density in the range 0,86-0.97 g/cm3, preferably in the range of 0.88 to 0,965 g/cm3more preferably in the range 0,3900-0.96 g/cm3even more preferably in the range 0,905-0.95 g/cm3nevertheless more preferably in the range 0,910-0,940 g/cm3most preferably more 0,915 g/cm3preferred more 0,920 g/cm3and most preferably more 0,925 g/cm3.

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 more than 1.5 to about 15, preferably from more than 2 to about 10, more preferably from more than about USA chromatography which in the art is well known.

In addition, the polymers according to the invention, as a rule, are characterized by a narrow compositional distribution as determined by the measure of the width of the compositional distribution (PSCR). The rest of the details determine PSCR copolymer specialists in this field known in the art (see, for example, in PCT application WO 93/03093, published on 18 February 1993, which fully included in the present description by reference.

In one embodiment, the polymers produced using metallocene catalyst of the type with the bulky ligand according to the invention have values PSCR, usually being in the range from more than 50 to 90%, preferably in the range of 55-85%, more preferably 60-80%, even more preferably greater than 60%, and yet more preferably more than 65%.

In another embodiment, the polymers produced using the catalyst of the conventional type with a transition metal, have PSCR less than 50%, preferably less than 40%, and most preferably less than 30%.

In one embodiment, the polymers of the present invention have a melt index (IR or 12), which is determined according to ASTM D-1238-is Erno 0.1 to about 50 DG/min, and most preferably from about 0.1 to about 10 DG/min

In one embodiment, the polymers according to the invention are characterized by the values of the ratio of the melt index (I21/I2) (I21determined according to ASTM D-1238-F) of from 10 to less than 25, preferably from about 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 (I21/I2) (I21determined according to ASTM D-1238-F) of from preferably greater than 25, more preferably greater than 30, even more preferably greater than 40, yet more preferably greater than 50, and most preferably more than 65.

In yet 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 and syndiotactic polypropylene. Other propylene polymers include propylene statistical, block - and high-impact copolymers.

The polymers obtained according to the method according to the invention can be used in such molding processes as extrusion and co-extrusion films and sheets and spinning fiber, as well as in the military blow moulding and casting, films made by joint extrusion layer and the 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, etc. 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 fiber for use in woven and non-woven forms in the manufacture of filter fabrics for towels, clothing, health care workers, geotextile materials, etc. Extruded products include tubes for medical purposes, covering of cables, geomembranes and facing materials for swimming pools. For molded products include single and multi-layer products in the form of bottles, tanks, large hollow articles, rigid containers for food, toys, etc.

EXAMPLES

For a better understanding of the entity to The properties of the polymer were determined by the following test methods:

The density was determined according to ASTM D-1238.

Contamination factor in the following tables illustrates the efficiency of the catalyst. The higher the value, the greater the observed pollution. Zero pollution, indicates almost complete lack or absence of visible contamination. Contamination factor 1 indicates light pollution, when the blades of the stirrer 2-liter reactor for suspension polymerization of isobutene is formed very weak discontinuous polymeric coating and/or on the housing reactor no sediment is formed. Contamination factor 2 indicates a more serious pollution, when the blades of the stirrer is formed thicker, resembling a layer of paint coating of the polymer, and/or on the vessel wall is formed by any deposition in the form of stripes with a width of 1-2 inches (2.54-5.08 cm). Contamination factor of 3 is considered as indicating the average contamination when the blade of the stirrer has a thicker latokartano coating of polymer in the reactor contains a number of soft lumps and/or on the vessel wall is formed by the deposition in the form of wide strips of 2-3 inches (5.08-7.62 cm). Indicator Zagra the covering, the reactor contains a number of more solid lumps/balls of polymer and/or on the vessel wall has a deposition in the form of a strip with a width of 3-4 inches (7.62-10.2 cm).

Specified in the following tables activity was determined in grams of polyethylene per gram of the polymerization catalyst per hour (g PE/g cat·h).

COMPARATIVE EXAMPLE 1

The preparation of the catalyst AND

Used in this comparative example 1 bridge catalytic metallocene compound type with the bulky ligand is dimethylsilane(tetrahydroindene)zirconiated [IU2Si(H4-ind)2Zrl2] available on the company Albemarle Corporation, Baton Rouge, PCs Louisiana. This catalytic compound [IU2Si(H4-ind)2Zrl2] was applied to silica varieties Crosfield ES-70, dehydrated at 600° C, the loss of moisture which when annealed (PVP) was approximately 1.0 wt.%. PVP is determined by the weight loss of the material carrier, which is heated and maintained at a temperature of about 1000° C. for about 22 hours, the Average particle size of silicon dioxide varieties Crosfield ES-70 is equal to 40 μm, it is available on the company Crosfield Limited, Warrington, Emistim ligand on the media includes the preparation of a solution of the precursor. 460 Lbs (209 kg) treated by bubbling and dried toluene is introduced into the reactor with mixer, then add 1060 pounds (482 kg) solution methylalumoxane (MAO) in toluene concentration of 30 wt.% (available on the company Albemarle, Baton Rouge, PCs Louisiana). As a catalytic compound charged to the reactor 947 lbs (430 kg) of toluene solution dimethylsilane-bis(tetrahydroindene)zirconiated concentration of 2 wt.% and an additional 600 pounds (272 kg) of toluene. Then, the solution of the precursor was stirred at 80-100F (26,7-of 37.8 C) for one hour.

When mixing the specified solution of the precursor in the solution of the precursor is added slowly 850 lbs (386 kg) dehydrated at 600C kremmidiotis media Crosfield and the mixture is stirred for 30 minutes at 80-100° F (26,7-Of 37.8 C). After 30-minute stirring mixture of 240 pounds (109 kg) of toluene solution of AS-990 (N,N-bis(2-hydroxyethyl)octadecylamine,18H37N-(CH2CH2OH)2] available in the form of product Kemamine AS-990 on the company Witco Corporation, Memphis, PCs Tennessee, a concentration of 10 wt.% together with an additional 110 lbs (50 kg) toluene wash liquid and then the contents of the reactor permissiveness for polymerization dried at 175F (S) for about 15 h to obtain engineering powder. The final weight of the polymerization catalyst is 1200 pounds (544 kg), the content of Zr in it and 0.35 wt.%, and Al - 12.0 wt.%.

EXAMPLE 1

Preparation of catalyst B

1-Kilogram sample sample of a polymerization catalyst prepared similarly to comparative example 1, a catalyst And in an inert atmosphere loaded into a 3-liter glass flask. Under vacuum at 85C dried 40 g of the product of Witco Aluminum Stearate #22 (AlSt #22) [CH3(CH2)16SOO]2-Al-HE], available on the company Witco Corporation, Memphis, PCs Tennessee, loaded into the flask and the contents will galuut/stirred for 20 min at room temperature. The aluminum stearate is evenly dispersed among the catalytic particles.

EXAMPLE 2

The preparation of the catalyst IN

1-Kilogram sample sample of a polymerization catalyst prepared similarly to comparative example 1, a catalyst And in an inert atmosphere loaded into a 3-liter glass flask. Under vacuum at 85C dried with 20 g of the product of Witco Aluminum Stearate #22 (AlSt #22) [CH3(CH2)16COO]2-Al-OH], which is available on the company Witco Corporation, Memphis, PCs Tennessee, loaded into the flask and the contents will galuut/parametrize catalytic particles.

EXAMPLE 3

Preparation of catalyst G

1-Kilogram sample sample of a polymerization catalyst prepared as described in comparative example 1, a catalyst And in an inert atmosphere loaded into a 3-liter glass flask. Under vacuum at 85C dried 10 g of the product of Witco Aluminum Stearate #22 (AlSt #22) [CH3(CH2)16COO]2-Al-OH], which is available on the company Witco Corporation, Memphis, PCs Tennessee, loaded into the flask and the contents will galuut/stirred for 20 min at room temperature. The aluminum stearate is evenly dispersed among the catalytic particles.

Polymerization process using catalysts a-D

Nitrogen purging in a 2-liter autoclave reactor load of 0.16 mmole of triethylaluminum (TEAL), and then 20 ml of hexene-1 as co monomer and 800 ml of isobutane diluent. The contents of the reactor are heated to 80 ° C, and then 100 mg of each of the above-mentioned polymerization catalysts on the media, catalysts a, B, C and D, separately injected into the polymerization processes in the following way: each polymerization catalyst is introduced into the reactor simultaneously with ethylene so that the total pressure in the reactor DOS is an increase of 40 minutes After 40 min, the reactor is cooled, ethylene discharged into the atmosphere, the polymer is dried and weighed to determine yield. The following table 1 shows the obtained activity data, as well as the characteristics of the contamination observed in the application of the catalyst And without aluminum stearate and catalysts B-G, each of which contains different amounts of aluminum stearate.

The data in table 1 illustrate the effect of varying amounts of aluminum stearate on the catalytic activity and efficiency.

COMPARATIVE EXAMPLE 2

Preparation of catalyst D

A 2-gallon (EUR 7.57 l) reactor first load of 2.0 l of toluene, then 1060 g methylalumoxane solution in toluene (available on the company Albemarle, Baton Rouge, PCs Louisiana) concentration of 30 wt.%, after that, 23.1 g of bis(1,3-methyl-n-butylcyclopentadienyl)zirconiated in the form of a 10% solution in toluene. The mixture is stirred for 60 min at room temperature, after which the fluid under slow stirring, 850 g of silica (Davison 948, dehydrated at 600° C, available on the company W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland). The mixing speed increase priblizilsia amount of toluene to prepare a slurry containing liquid and solids 4 cm3/g of silica. Mixing continued for 15 min at a speed of 120 Rev/min, after which 100 ml of toluene was dissolved 6 g of the product Kemamine AS-990 (available on the company Witco Corporation, Memphis, PCs Tennessee) and stirred for 15 minutes Then under vacuum and at a certain purging with nitrogen at 175F (79,4 C) initiate drying. When a polymerization catalyst comprising a carrier, silicon dioxide, is engineering, it is cooled and discharged in a nitrogen purged vessel. Due to some losses in the drying reach the exit of the dry curing catalyst approximately 1 kg.

EXAMPLE 4

Preparation of catalyst E

A sample of the polymerization catalyst, prepared as described in comparative example 2, catalyst D, mixed in a dry state with so many product Witco Aluminum Stearate #22 (AlSt #22, available on the company Witco Corporation, Memphis, PCs Tennessee), which is equal to 2 wt.% in terms of the total weight of the polymerization catalyst on the carrier. Product AlSt #22 is dried in a vacuum oven for 12 hours at 85C. Next, in a nitrogen atmosphere and polymerization catalyst are mixed in a dry state with the product AlSt #11. The data in table 2 demon in the polymerization catalyst. This example also shows that the carboxylate salt of the metal at the molecular-mass characteristics of the obtained polymer no effect.

The results of the experiments with polymerization catalysts D and E using the same method as described above for catalysts a-D below in table 2.

COMPARATIVE EXAMPLE 3

The preparation of the catalyst W

A 2-gallon (EUR 7.57 l) reactor load 1060 g of the solution methylalumoxane (MAO), activator in toluene (PMAO, modified MAO, available on the company Akzo Nobel, Laporte, pc. Texas) concentration of 30 wt.%, and then 1.5 l of toluene. With stirring the reactor was added 17.3 g of bis (1,3-methyl - n - butylcyclopentadienyl) zirconiated, catalytic metallocene compound type with the bulky ligand, in the form of a solution in toluene concentration of 8 wt.% and at room temperature the mixture is stirred for 60 min, obtaining a solution of the catalyst. The contents of the reactor are discharged into the flask and charged to the reactor 850 g of silica dehydrated at 600° C (available on the company Crosfield Limited, Warrington, England). Further contained in the flask the catalyst solution is added slowly to kranidioti add an additional 350 ml of toluene and the mixture is stirred for another 20 minutes Add 6 g of the product Kemamine AS-990 (available on the company Witco Corporation, Memphis, PCs Tennessee) in toluene solution concentration of 10 wt.% and stirring is continued at room temperature for 30 minutes and Then the temperature was raised to 68° C (155° F) and apply vacuum with the purpose of dry-curing catalyst. Drying continued at low speed mixing for about 6 hours, up until the polymerization catalyst is not engineering. Further, it is discharged into the flask and stored in an atmosphere of N2. Due to some losses in the drying process, the output is 1006, According to the analysis, this polymerization catalyst includes a 0.30 wt.% Zr, and 11.8 wt.% Al.

EXAMPLES 5 AND 6

In examples 5 and 6 polymerization catalyst prepared similarly to comparative example 3, the catalyst W, Inuktitut together with 4 and 8 wt.% product Witco Aluminum Stearate #22 (AlSt #11), available on the company Witco Corporation, Memphis, PCs Tennessee, in terms of the amount of catalyst injected into the polymerization reactor. The results of the experiments with polymerization using catalysts W, 3 and using the same method as described above for catalysts a-D, presents neither the AE highly active catalyst, more prone to the formation of impurities. In addition, they show that the aluminum stearate product material does not change.

EXAMPLES 7-11

In examples 7 and 8 use the same catalyst as in comparative example 3, the catalyst W, together with calcium stearate (CaSt) (catalyst K) as a carboxylate metal salt in example 7, and zinc stearate (ZnSt) (catalyst L) in example 8. Products CaSt and ZnSt is available on the company Mallinkrodt Corporation, Phillipsburg, PCs new Jersey. The method of polymerization, which is used for testing the catalytic compositions 7 and 8, similar to those described above and applied catalysts A-Year

In examples 9-11 are using the same catalyst as in comparative example 1, the catalyst And, together with aluminium monostearate (example 9, the catalyst M) as a carboxylate metal salt, distearate aluminum (example 10, the catalyst N) and tristearate aluminum (example 11, the catalyst was About). The last of the presents in the present description and used in examples 12-15 method of polymerization used for testing the catalytic compositions of examples 9-11, catalysts M, N and O. the results are presented below in table 4.

EXAMPLES 12-15

In examples 12-15 method of dry mixing, described in example 1 is used with respect to the catalyst And comparative example 1 in combination with carboxylate salts of metals of different types. The number and type of carboxylate metal salt shown in table 5. For each combination of a polymerization catalyst/carboxylate salt of the metal catalyst P, R, s and T, is applied next, described below is a method of polymerization.

The method of polymerization in examples 12-15

A 2-liter autoclave reactor in a stream of nitrogen load of 0.16 mmole of triethylaluminum (TEAL), and then 25 ml of hexene-1 as co monomer and 800 ml of isobutane diluent. The contents of the reactor are heated to 80 ° C, and then 100 mg of each of the mixtures described above polymerization catalysts carboxylate salts of the metals on the carrier, a catalyst And listed in table 5 amounts of carboxylate metal salt) separately in Etna salt of the metal is injected into the reactor simultaneously with ethylene so, to the total pressure in the reactor reached 325 psi (2240 kPa). The temperature of the reactor is maintained at the level 85C and conduct polymerization for 40 min after 40 min, the reactor is cooled, ethylene discharged into the atmosphere, the polymer is dried and weighed to determine yield.

The following table 5 shows the results obtained. Of particular interest is the fact that examples 12, 13, 14 and 15 illustrate the preference for having a carboxylate metal salt bulky group R, and specifically aluminum carboxylates.

EXAMPLES 16 to 18 AND COMPARATIVE EXAMPLE 4

Examples 16, 17 and 18 and comparative example 4 illustrate the effectiveness of carboxylate metal salt, in particular of aluminum stearate, gas-phase process with fluidized bed in combination with the catalyst system of the metallocene type with the bulky ligand upon receipt of the polymers of those varieties, which typically receive more significant difficulties, especially in the technological field. From the viewpoint of operability of the reactor products are those varieties that have a fractional melt index and higher density, traditionally the polymerization of examples 16, 17 and 18 and comparative example 4, was tested under the implementation of the method described below; the results are presented in the following table 6.

The method of polymerization

Further catalysts a, B and E, described above, separately experience in gas-phase reactor of continuous fluidized bed, which is a nominal 18-inch reactor for process mode 60 with an inner diameter of 16.5 inches (41,9 cm). A fluidized bed of polymer granules. Gaseous streams of the ethylene feedstock and hydrogen with liquid co monomer are mixed together in mixing tee device and through the line for recycle gas is introduced into the reactor below the layer. As co monomer used hexene-1. The flow rate of ethylene, hydrogen and co monomer regulate individually in such a way as to maintain a constant target composition. To maintain a constant partial pressure of ethylene regulate the concentration of ethylene. To maintain a constant molar ratio between hydrogen and ethylene regulate the concentration of hydrogen. Concentration of all the gases is determined using mounted on technological Lin is th catalytic system metallocene type with the bulky ligand, supported on a carrier, specified in table 6, Inuktitut directly into the fluidized bed using purified nitrogen with a flow rate of 1.5 lb/h (0.68 kg/h). The reaction layer of the growing polymer particles supported in a fluidized bed state of the constant current source materials and recycle gas stream passing through the reaction zone. For this purpose apply the gas flow rate per unit cross section of the thread 1-3 ft/s (up to 30.5-91.4 cm/s). The reactor operates under a total pressure of 300 psig (2069 kPa), the reaction temperature is 85C, and to ensure fluidization of the granules used the gas flow rate per unit cross section of flow of 2.25 ft/s (68.6 cm/s). To maintain a constant reaction temperature continuously regulate the temperature of the recycle gas, which increase and decrease in accordance with all changes of number of eye-catching due to the polymerization heat. The constant height of the fluidized bed to support the removal of this layer in an amount which is equal to the resultant powdery product. The product removes semi-continuous with a series of valves in the chamber of fixed volume, which also communicates with the reactor through tushie a significant portion of the unreacted gases. The product is rinsed to remove carry out with him hydrocarbons and process weak current humidified nitrogen for decontamination of all trace quantities of residual catalyst.

The use of carboxylate metal salt in combination with a polymerization catalysts allows to dramatically improve the efficiency of the reactor. Data in table 6 illustrate the operation of gas-phase reactor without the occurrence of any problems in obtaining polymers with a fractional melt index at many values of appealability layer (ABOUT. Shows in particular that the use of a polymerization catalyst without a carboxylate metal salt, as in comparative example 4 (without aluminum stearate), leads to stopping of the reactor due to pollution and sedimentation after less than 3 turns of the layer with a melt index of about 1.5 DG/min and density 0,9188 g/cm3. In the embodiment of the invention, the process continued for a period corresponding to more than 4 turns of the layer, more preferably more than 5 turnovers layer, and most preferably more than 6 turnovers layer. Turnover layer is completed when the total mass of the polymer discharged from the reactor, reducing the bulk weight of the resin improves the efficiency of the polymerization process, in particular, gas-phase polymerization process in the fluidized bed. When evaluating the data from the table 6 it can be noted that the volumetric weight of the resin does not change substantially, however, when the polymerization catalyst is used in combination with a carboxylate metal salt, the efficiency of the process carried out according to the invention is unexpectedly improved.

EXAMPLE 19

The preparation of the catalyst of conventional type with transition metal

The catalyst of the conventional type with transition metal is prepared in General from a mixture of compounds of magnesium, such as MgCl2, titanium compounds, for example il3·1/3 ll3and an electron donor, such as tetrahydrofuran (THF), and applied on the silicon dioxide, which are dehydrated at 600C. Detailed description of the method of preparation can be found in US patent No. 4710538, which is included in the present description by reference. Specifically used catalytic composition is characterized by the values of the molar ratio TNGAL/THF 29 and molar ratio DEAH/THF 26, where TNGAL means tri-n-hexylamine and DEAH means diethylaluminium.

Polymerization process using the catalyst of the conventional type with periodperiod actions fluidized bed, which is a nominal 18-inch (45.7 cm) reactor for the process mode 60 with an inner diameter of 16.5 inches (41,9 cm), as presented above in the present description. Apply the same method and conditions as specified above. However, in conducting this process in the reactor is continuously injected solution triethylaluminium (TEAL) socializaton conventional type in hexane concentration of 5 wt.%, that allows you to maintain the content TEAL in the fluidized bed of approximately 300 ppm million Directly into this fluidized bed Inuktitut solid catalyst conventional type with a transition metal, prepared as described directly above (see experiment And table 7).

Prepare a solution of carboxylate metal salt, a product of Witco Aluminum Stearate # 22 (AlSt #22) in hexane (2000 ppm million). During the polymerization process (see experiment And table 7) this solution is injected into the gas-phase reactor (see results of experiment B in table 7). According to the material balance, the performance of this catalyst remains essentially the same even after the addition of aluminum stearate. Moreover, in this example, the efficiency of the reactor is maintained in the period aprivately example shows that the application of the carboxylate metal salt in combination with a catalytic system of the usual type with a transition metal on the efficiency of the continuous gas-phase polymerization has no impact, particularly when the carboxylate metal salt is administered separately from the catalyst system of the usual type. However, as it was found, in the course of some experiments with batch suspension polymerization product application Witco Aluminum Stearate varieties EA, which in the dry state is mixed with conventional type catalyst containing as the metal titanium, leads to performance degradation. Not based on any theory, it is believed that this decrease in performance can be partly caused by the interaction of aluminum stearate with socialization conventional type, for example with triethylaluminium, resulting in a batch reactor, the produced less active socialization.

The following examples 20 and 21 illustrate the application of the conventional type catalyst containing as the metal chromium mixed in the dry state with a carboxylate metal salt.

EXAMPLE 20

Prepared the as containing a series of metal chrome, also known as the catalyst type catalyst of the Phillips company, prepared using the catalyst Crosfield EP510 (1 wt.% titanium and 0.5 wt.% chromium in the form chromatiaceae), available on the company Crosfield Limited, Warrington, England. The catalyst EP510 activate at 800C using 70% oxygen/30% nitrogen in the column of fluidized bed, as it is known in the art, and are used in the following polymerization process.

COMPARATIVE EXAMPLE 20A

The process of homopolymerization ethylene

In the autoclave of a capacity of 2.2 l as a cleaning additive to remove traces of impurities injected in the vessel 100 mcmole of triethylaluminum (25 wt.% TEAL in the form of a solution in heptane). In the reactor is injected 800 ml of isobutane varieties for polymerization available for Phillips Petroleum, Bartlesville, PCs Oklahoma. The contents are stirred at a speed of 1000 rpm and the reactor temperature increase from room temperature up to 93S, and then ethylene is injected into the reactor until the excess pressure in the reactor 375 psig (2586 kPa).

Then charged to the reactor 300 mg of activated chromium catalyst prepared in the above example 20, and for about 60 min conducting the polymerization of ethylene, after che is the catalyst, as stated above, used in its pure form (without aluminum stearate), resulting in a gain vysokozaraznoy static electricity polymer. To remove a charged static electricity polymer from the walls of the reactor should be used hexane solution of antistatic agent Kemamine AS-990. The total number of the collected resin is about 245,

EXAMPLE 20B

In this example, prior to polymerization a polymerization catalyst comprising 300 mg of activated chromium catalyst (prepared analogously to the above example 20), mixed in a dry state with 15 mg of aluminum stearate, product Witco Aluminum Stearate varieties EA. Further, this polymerization catalyst loaded into the reactor under the same polymerization conditions as shown in comparative example 20A. After 60 minutes the polymerization stop and inspect the reactor. The obtained resin by static electricity is not charged, and it is easily removed from the reactor. The yield of tar is equal to 133, This experiment shows that the carboxylate salt of the metal, luminescente connection or prevents the accumulation or neutralizes the charge on the resin obtained by using a catalytic system obecnie sediments in the process of gas-phase polymerization of ethylene using chromium catalyst is associated with the accumulation in the system of static charge.

EXAMPLE 21

The process of copolymerization

In the reactor as a cleaning additive to remove traces of impurities injected in the vessel 50 mcmole of triethylaluminum. After that, the reactor is injected 50 ml of purified 1-hexene as co monomer and 800 ml of isobutane. After raising the reactor temperature to 85C under stirring at a speed of 1000 rpm in a vessel, introducing ethylene to achieve excess pressure of 325 psig (2586 kPa). Then charged to the reactor 300 mg of a polymerization catalyst and for some period of time, the polymerization process. Then the reaction complete discharge of hydrocarbons from the reactor into the atmosphere. In all the following examples use this method of polymerization. However, in some examples, the amount of hexene-1 and the reaction time vary.

COMPARATIVE EXAMPLE 21A

Charged to the reactor 300 mg of activated chromium catalyst, a polymerization catalyst, and similarly to the above example 21 for approximately 60 min conducting the polymerization process. In this comparative example 21A chromium catalyst used in its pure form, without aluminum stearate, resulting in pollution. On the wall of the reactor, the stirrer and vnutrennyaya in the form of lumps. The total number of the collected adhesive resin is g.

EXAMPLE 21B

In this example, 300 mg of activated chromium catalyst prepared in the above example 20, in the dry state is mixed with 15 mg of aluminum stearate, product Witco Aluminum Stearate varieties EA. Used polymerization method described in the above example 21. After 50 min the experiment terminates the discharge of hydrocarbons into the atmosphere. Contamination of the reactor, as installed, is much smaller than in comparative example 21A. On the stirrer, thermocouple and the wall of the reactor noted the presence of a thin visible polymeric coatings. The total number of the collected resin is approximately 110 g

COMPARATIVE EXAMPLE 21B

In comparative example 21B polymerization process carried out analogously to example 21, except that they use 35 ml of 1-hexene. 300 mg of this activated chromium catalyst as described above in example 21, used in its pure form, without aluminum stearate. The polymerization is carried out in a period of 50 min, and then the gases from the reactor is discharged into the atmosphere and inspect. Note the severe pollution of the reactor. In the upper part of the reactor is formed by a ring of polymer I reactor noted the presence of polymer deposits. The total number of the collected resin is approximately 139, the Polymer is too comcouncil to determine the density of the product.

EXAMPLE 21G

In this example, the polymerization process is conducted as in example 21, except that they use 35 ml of 1-hexene. 300 mg of this activated chromium catalyst as used in comparative example 21B, in dry form is mixed with 15 mg of aluminum stearate, product Witco Aluminum Stearate varieties EA. The polymerization is carried out in a period of 50 min, and then the gases from the reactor is discharged into the atmosphere and inspect. On the stirrer, thermocouple and the wall of the reactor noted the presence of a very thin polymer coating. The polymer yield is equal to 139 g and the density is 0,9282 g/cm3.

In one embodiment, the object of the invention is a method for the continuous polymerization of ethylene and at least one alpha-olefin containing 3 to 20 carbon atoms, in the presence of a polymerization catalyst comprising the catalyst of conventional type, as of metal containing chromium, and a carboxylate metal salt, to obtain the polymer product, the density of which is less 0,945 to about 0.910 g/cm3preferably less 0,940 grolee preferably less 0,92 g/cm3. In a preferred embodiment, a continuous process is a gas-phase process is conducted at a pressure from about 200 to about 400 pounds per square inch (1379-2759 kPa) and at temperatures from above 60C, preferably from 70 to about 120C, and in the preferred embodiment, the gas-phase process is conducted in the condensate, when in a reactor with a fluidized bed comprising pseudovirus environment, introducing the liquid and the gas, and when the content of the condensed fraction exceeds 8 wt.%, preferably more than 10 wt.%, and most preferably ranges from greater than 12 to 50 wt.% in terms of the total weight of pseudoviruses medium entering the reactor. For more details of the method, carried out with the condensate, you should contact the US patents No. 5342749 and 5436304, which are both fully incorporated in the present description as a reference.

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 choices that illustrated in the present description is not necessary. So, for example, adding in the reactor of the invention. There is also the possibility of applying the method according to the invention in a polymerization process carried out in several reactors. Thus, in particular, in a single reactor is used supported on a carrier of the catalytic system of the metallocene type with the bulky ligand that does not include carboxylate metal salt and the other is used supported on a carrier bridge catalytic system metallocene type with the bulky ligand in contact with the carboxylate metal salt and Vice versa. In addition, there's even the possibility of introducing into the reactor or polymerization catalyst of the initial components for the carboxylate metal salt, carboxylic acids and metal joints, such as a metal hydroxide, obtaining in situ in the reactor or in conjunction with this catalyst. You can also separate application to the media carboxylate metal salt, separately from the polymerization catalyst, preferably a polymerization catalyst on the carrier. For this reason, in order to determine the actual scope of the present invention, reference should be made only on the enclosed claims.

1. Catalytic composition for the polymerization of olefins, containing misty ligand, and a carboxylate metal salt, which corresponds to the formula

MQx(OOCR)y,

where M denotes a metal atom of group III of the Periodic table;

Q denotes hydroxyl;

R is a hydrocarbon radical containing 2-100 carbon atoms;

x denotes an integer of 1 or 2;

y denotes an integer of 1 or 2, and the sum of x and y is equal to the valence of the metal,

moreover, the mass percentage of carboxylate metal salt, calculated on the total weight of the polymerization catalyst is in the range of 0.5 to 100 wt.%.

2. The catalytic composition under item 1, where in the formula of the salt R denotes a hydrocarbon radical containing 4-24 carbon atoms.

3. Catalytic composition for p. 2, where in the formula of the salt R denotes a hydrocarbon radical containing more than 12 carbon atoms.

4. The catalytic composition according to any one of the preceding paragraphs, in which the melting temperature of the carboxylate metal salt is 100-200C.

5. The catalytic composition according to any one of the preceding paragraphs, in which the carboxylate metal salt is stearate connection, preferably aluminium what toroi polymerization catalyst is a polymerization catalyst on the carrier, includes carrier, preferably an inorganic or organic carrier, preferably an inorganic carrier, and most preferably an inorganic oxide.

7. The catalytic composition according to any one of the preceding paragraphs, in which the polymerization catalyst further comprises a carrier, an activator, preferably alumoxane and catalytic metallocene compound type with the bulky ligand contains an atom of titanium, zirconium or hafnium.

8. The catalytic composition according to any one of the preceding paragraphs, in which the catalytic metallocene compound type with the bulky ligand corresponds to the formula

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

in which M denotes a transition metal of group IVa, Va or VIa;

(C5H4-dRd) denotes unsubstituted or substituted derivationally from bulky cyclopentadienyl ligand bound to M;

each R, which may be identical or different, denotes a hydrogen atom or a group substituent containing up to 50 non-hydrogen atoms, substituted or unsubstituted hydrocarbon containing 1-30 carbon atoms, or combinations thereof is displaced ring or ring system, containing 4-30 carbon atoms;

And denotes a radical containing one or more, or a combination of atoms of carbon, germanium, silicon, tin, phosphorus and nitrogen linking bridge coupling the two rings (C5H4-dRd);

each of Q, which may be identical or different, denotes a hydride, substituted or unsubstituted linear, cyclic or branched hydrocarbon containing 1-30 carbon atoms, a halogen atom, alkoxides, aryloxides, amides, phosphides, or any other univalent anionic ligand or a combination thereof; two groups Q may also be formed alkylidene ligand or cyclometalation hydrocarbon ligand or other divalent anionic chelating ligand;

g denotes an integer corresponding to the formal oxidation state of M, d denotes an integer selected from 0, 1, 2, 3 and 4, and indicates the degree of substitution;

x denotes an integer of 0 or 1.

9. The catalytic composition according to any one of the preceding paragraphs, in which the content of carboxylate metal salt, calculated on the total weight of the polymerization catalyst is in the range of 1-50 wt.%, and more preferably from more than 1 Audiusa points, which can be prepared by the method comprising (a) preparing a polymerization catalyst and (b) adding at least one carboxylate metal salt.

11. The catalytic composition according to any one of the preceding paragraphs, which can be prepared according to the method, including the introduction of dry and engineering a polymerization catalyst comprising a catalytic metallocene compound type with the bulky ligand in contact with the carboxylate metal salt in solid form.

12. The method of preparation of the catalytic composition according to any one of the preceding paragraphs.1-10, which includes mixing a polymerization catalyst comprising a catalytic metallocene compound type with the bulky ligand, with a carboxylate metal salt.

13. The method according to p. 12, in which the period of mixing is from 1 min to 12 hours

14. The method according to p. 12 or 13, in which the duration of mixing is from 10 min to 10 h, preferably from 30 minutes to 8 o'clock

15. Method for continuous polymerization, which involves feeding into the reactor a catalytic composition according to PP.1-11 and olefinic monomers to obtain a polymer product.

16. The way nepreryvnoi the composition of PP.1-11.

17. The method of gas-phase or continuous suspension polymerization of olefins in a reactor in the presence of a catalytic composition according to PP.1-11.

18. Method for continuous polymerization of olefin monomers in the reactor at polymerization conditions including the following stages: (a) the introduction of olefin monomer(monomers) into the reactor; (b) the introduction of a catalytic composition according to PP.1-11 and (C) removing from the reactor the polymer product.

19. The method according to p. 18, in which the process is suspended.

20. The method according to p. 18, in which the process is a gas phase.

21. Method for continuous gas-phase polymerization of the monomers in the 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 a catalytic composition according to PP.1-11; (C) the removal 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.

22. Method for continuous gas-phase polymerization et the population in the range of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), when the polymerization temperature in the range of from about 70 to about 110S, in the performance of more than 10,000 pounds (4540 kg) of polymer product per hour and when the performance of a polymerization catalyst 1500 g of polymer product per gram of the polymerization catalyst, and the process is carried out in the presence of a polymerization catalyst comprising a catalytic metallocene compound type with the bulky ligand and the carboxylate metal salt, which corresponds to the formula

MQx(OOCR)y,

where M denotes a metal atom of group III of the periodic table;

Q denotes hydroxyl;

R is a hydrocarbon radical containing 2-100 carbon atoms;

x denotes an integer of 1 or 2;

y denotes an integer of 1 or 2, and the sum of x and y is equal to the valence of the metal,

moreover, the mass percentage of carboxylate metal salt, calculated on the total weight of the polymerization catalyst is in the range of 0.5 to 100 wt.%.

23. The method according to p. 22, where in the formula of the salt R denotes a hydrocarbon radical containing 4-24 carbon atoms.

24. The method according to p. 23, where in the formula of salt about R-24, in which the melting temperature of the carboxylate metal salt is 100-200C.

26. The method according to any of paragraphs.18-25, in which the carboxylate metal salt is stearate connection, preferably aluminiumfenster or aluminiumstearate.

27. The method according to any of paragraphs.18-26, in which the polymerization catalyst comprises a carrier, an activator, preferably alumoxane, and catalytic metallocene compound type with the bulky ligand containing an atom of titanium, zirconium or hafnium.

28. The method according to any of paragraphs.18-27, in which the catalytic metallocene compound type with the bulky ligand corresponds to the formula

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

in which M denotes a transition metal of group IVa, Va or VIa;

(C5H4-dRd) denotes unsubstituted or substituted derivationally from bulky cyclopentadienyl ligand bound to M;

each R, which may be identical or different, denotes a hydrogen atom or a group substituent containing up to 50 non-hydrogen atoms, substituted or unsubstituted hydrocarbon containing 1-30 carbon atoms, or the aqueous or unsubstituted ring or ring system, containing 4-30 carbon atoms;

And denotes a radical containing one or more, or a combination of atoms of carbon, germanium, silicon, tin, phosphorus and nitrogen linking bridge coupling the two rings (C5H4-dRd);

each of Q, which may be identical or different, denotes a hydride, substituted or unsubstituted linear, cyclic or branched hydrocarbon containing 1-30 carbon atoms, a halogen atom, alkoxides, aryloxides, amides, phosphides, or any other univalent anionic ligand or a combination thereof; two groups Q may also be formed alkylidene ligand or cyclometalation hydrocarbon ligand or other divalent anionic chelating ligand;

g denotes an integer corresponding to the formal oxidation state M;

d denotes an integer selected from 0, 1, 2, 3 and 4, and indicates the degree of substitution;

x denotes an integer of 0 or 1.

29. The method according to any of paragraphs.18-28, in which the mass percentage of carboxylate metal salt, calculated on the total weight of the polymerization catalyst is in the range of 1-50 wt.%, and more preferably from more than 1 maiese receive the polymer product, with a value of I21/I2more than 30, in the preferred embodiment, the mass percentage of at least one carboxylate metal salt exceeds 1 in terms of the total weight of at least one polymerization catalyst, and the density of the polymer product is 0.910 g/cm3.

31. The method according to p. 28, in which x denotes 1, and in the process get a propylene homopolymer or propylene copolymer.

32. The method according to any of paragraphs.18-29, in which the density of the polymer product exceeds 0,920 g/cm3and the value of I21/I2more than 30, preferably in which the density of the polymer product exceeds 0,925 g/cm3and the value of the melt index less than 1 DG/min.

33. The method according to any of paragraphs.18-32, in which the carboxylate metal salt introduced into the process continuously or intermittently.

34. The method according to p. 22, in which the performance exceeds 25000 pounds of polymer product per hour (11340 kg/h).

35. The method according to any of paragraphs.21-34, in which the process is a gas-phase process for obtaining a polymer product, the density of which exceeds 0,920 g/cm3and a melt index equal to less than about 1 DG/min, predpochtitel equal to less than 0.75 DG/min

36. The method according to any of paragraphs.18-35, in which before adding to the reactor carboxylate metal salt introduced into contact with the polymerization catalyst.

37. The use of carboxylate metal salt in the composition of the catalytic composition on the PP.1-11 to reduce pollution and/or sedimentation during the gas-phase polymerization process or polymerization process in suspension phase, preferably a continuous gas-phase polymerization process.

 

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