Component of the catalyst on the carrier, the catalyst on the carrier, the method of its production and the way polyaddition

 

(57) Abstract:

The invention relates to the preparation of catalyst components on the carrier, including a carrier and alumoxane, the catalysts on the media containing the metallocene compound and the ways polyaddition using these catalysts. The catalyst on the carrier contains a compound of a transition metal and a component consisting of a carrier and alumoxane. Alumoxane contains 15-40% aluminum by weight of the total carrier and alumoxane, with not more than 10 wt.% aluminum extracted for one hour at 90°C using 10 ml of toluene, 1 g of the catalyst component on the carrier. Component of catalyst is obtained by fixing alumoxane in the form of a free current of powder on the carrier by heating in an inert atmosphere at 75 - 250oC and washed out in one or more stages aromatic hydrocarbon solvent. When the connection is added to the transition metal so that the resulting product has not been subjected to temperatures equal to or higher than the temperature of decomposition of transition metal compounds, before or after heating of the specified component of the catalyst or after the stage of leaching get the catalyst to naseema clogging of the reactor, especially when gas-phase polymerization or suspension polymerization. 5 C. and 18 h.p. f-crystals, 11 PL.

The present invention relates to a component of the catalyst on a carrier, including a carrier and alumoxane, the catalyst on the carrier, including the media, alumoxane and metallocene compound, and the method of obtaining this component of the catalyst on the carrier and catalyst, and method polyaddition using catalyst on the carrier.

Background of the invention

Homogeneous or nenalezena alumoxane metallocene rolled congestion is known for its high activity olefin in polymerization. In the conditions of the polymerization when the polymer is formed in the form of solid particles, these homogeneous (soluble) catalysts formed by deposition of polymer on the walls of the reactor and stirring; these deposits should often be removed because they interfere with efficient heat sink required for cooling the contents of the reactor and cause premature wear of moving parts. The polymers obtained with the use of these catalysts, subsequently have low bulk density, which limits industrial use as polymer and method. For razresheniya in justiciarship methods of polymerization.

In Pat. USA 5057475 described alumoxanes metallocene catalyst on a carrier, where alumoxanes may be selling alumoxane or alumoxane obtained in situ on a solid medium, for example, adding connection trialkylamine to media containing water, in particular the addition of trimethylaluminum to contain water to silica. In preferred methods, U.S. Pat. USA 5057475 metallocene component and alumoxane (which previously may be connected with modifier) unite at the first stage, in a suitable solvent. At the next stage, this solution is in contact with the media. Then the solvent can be removed, usually in a vacuum. The solution can be heated, which helps to remove the solvent. In an alternative method negidrirovannah silica gel are added to a solution trialkylamine for education alumoxane, which is deposited on the surface of silica gel particles. Then the solvent is removed and the solid residue dried to free flowing powder. In typical examples, the dried silica is suspended with alumoxane in toluene, filtered, washed with pentane and then dried in vacuum. Metallocene compound is usually combined with alumoxane in toluene or heptane, in the vacuum and release the catalyst on the carrier.

In Pat. USA 5026797 describes the treatment of the particles of water insoluble inorganic oxide carrier alumoxane in solvent alumoxane, such as aromatic hydrocarbons, followed by rinsing the treated media aromatic hydrocarbon solvent prior to the termination detection alumoxane in the upper layer of sludge. Thus States that you can adjust the number of atoms of aluminum alumoxane attached to the oxide carrier in the range of 2 to 10 wt.%. Then the processed media combined with a compound of zirconium. Thus obtained carrier containing alumoxane and connection Zirconia, is used together with an additional amount alumoxane in the solution for polymerization reactions.

In Pat. USA 5147949 disclosed metallocene alumoxane catalysts on a carrier obtained by adding water-soaked catalyst carrier to stir the solution trialkylamine and the addition of metallocene component to the product of their interaction.

Pat. USA 5240894 describes a method of obtaining a catalyst on the carrier by education metallocen/alumoxane reaction solution, adding a porous medium, upar is athelney terpolymerization catalyst with the olefin monomer. Good bulk density of the polymer is achieved only with the use of terpolymerization catalyst on the carrier.

In Pat. USA 5252529 disclosed solid catalysts for olefin polymerization, comprising particles of a carrier containing at least 1 wt.% water alumoxane compound and a metallocene compound. For preparation of this catalyst is the product of the interaction of the particles of the medium and alumoxane by decantation separated from the diluent (toluene) or dried under reduced pressure.

In TU N 368644 disclosed a method of obtaining a metallocene alumoxane catalyst on the carrier on which negidrirovannah silica gel was added to a stirred solution of triethylaluminum, to this reaction mass is added a solution of metallocene, to which was added trimethylaluminum. After adding metallocene treated with trimethylaluminum, silica gel treated triethylaluminium, the catalyst is dried to a free flowing powder. Drying of the catalyst can be carried out by filtration or by evaporation of the solvent at a temperature of up to 85oC.

In TU N 323716 disclosed a method of obtaining a metallocene alumoxane illumine, add metallocene to this reaction mass, solvent removal and drying of the solid phase to a free flowing powder. After addition of metallocene remove the solvent, and the remaining solids are dried at temperatures up to 85oC.

TU N 523416 describes a component of the catalyst on the carrier for olefin polymerization obtained from inorganic media and metallocene. Metallocen and media intensively mixed in a solvent. Preferably, the thus obtained catalyst component is extracted with a suitable solvent, such as toluene, to remove nezavisimosgo metallocene. Then as socializaton can be added alumoxane.

TU N 567952 describes the polymerization catalyst on a carrier, comprising the reaction product alyuminiiorganicheskikh connection on the media and metallocene catalyst. This catalyst on the carrier receives the connection of trimethylaluminum with pre-dried carrier in inert aliphatic suspendida environment, to which was added water. Suspension may be used by itself or can be filtered, and thus obtained solid phase can be reused with the m Upon completion of the reaction the pooled solution is separated and the remaining solid phase is washed from 1 to 5 times the inert suspendida environment, such as toluene, n-decane, diesel oil or dichloromethane.

TU N 582480 describes a catalytic system on the media, including media and alumoxane where aluminum, located in the catalytic system on the media is partially extracted by talula at elevated temperatures.

You need to develop a catalyst component on the carrier, the catalyst on the carrier and the method of polymerization, which solves or substantially reduces the problem of clogging of the reactor, especially in gas-phase polymerization or suspension polymerization. Further, it is believed that the polymeric products produced by the methods of gas-phase polymerization or suspension polymerization, are free flowing form and preferably have a high bulk density.

Brief description of the invention

In one aspect the present invention provides a component of the catalyst on a carrier, including a carrier and alumoxane; this component contains from 15 to 40 wt.% aluminum from the General mass media and alumoxane, and not more than 10% of the aluminum in the component is La on 1 g of the component of the catalyst on the carrier. The specified component of the catalyst on the carrier receive

A. heating the medium containing alumoxane, in an inert atmosphere for a time and at a temperature sufficient to commit alumoxane on the media.

In another aspect provides a catalyst on a carrier, comprising the catalyst component on the carrier, in accordance with the present invention, and the compound of the transition metal containing at least one cyclic or acyclic-linked anionic ligand.

According to further aspect provides a method of obtaining a catalyst component on the carrier, including

A. heating the media containing alumoxane, in an inert atmosphere for a time and at a temperature sufficient to commit alumoxane on the media through which the selecting conditions for warming up on stage And receive the component, which contains from 15 to 40 wt.% aluminum from the General mass media and alumoxane, and not more than 10% of the aluminum in the component of the catalyst on the carrier, extracted with toluene at 90oC for 1 hour using 10 ml of toluene, 1 g of the catalyst component on the carrier.

In another aspect the invention provides a method Poluchenie over time and at a temperature sufficient for fixing alumoxane on the carrier; and optionally followed

B. stages of leaching containing alumoxane media from 1 to 5 times to remove alumoxane, not zafiksirovalos on the media, selecting conditions for warming up on stage and optional washing stage B. thus, to obtain a catalyst component on the carrier, which contains from 15 to 40 wt.% aluminum from the General mass media and alumoxane, and not more than 10% of the aluminum in the component of the catalyst on the carrier, extracted with toluene at 90oC for 1 hour using 10 ml of toluene, 1 g of the catalyst component on the carrier; and

adding before or after stage a or B transition metal compounds containing at least one cyclic or acyclic-linked anionic ligand, provided that from the moment of addition of the transition metal compounds thus obtained product is not exposed to temperatures equal to or greater than the decomposition temperature of the compound of the transition metal.

In another aspect provides a method polyaddition, where one or more politicoeconomic monomers in contact with the catalyst on the carrier, Soglasie references to elements or metals, belonging to a particular group, refer to the Periodic table of the elements, published by CRC Press, Inc. in 1989 and copyrighted. Also, any reference to a group or groups should be done on a group or groups specified in this Periodic table of the elements, using the numbering of the groups according to the IUPAC system. Used herein, the term "hydrocarbon" means any aliphatic, cycloaliphatic, aromatic group, or any combination thereof. The term "hydrocarbonate" means hydrocarbon, which are linked through oxygen between it and the element to which it is attached. If the description and the claims the expression "substituted cyclopentadienyl, it includes substituted in the ring or polynuclear derivatives cyclopentadienyls particles, where these substituents include hydrocarbon, hydrocarbonate, gidrokarbanatno, CYANOGEN, halogen, silyl, germyl, siloxy or mixtures thereof, or two of such substituent are hidrocarburos group; specified Deputy (or two Vice-together) have up to 30 atoms in addition to hydrogen atoms. The term "substituted cyclopentadienyl" includes, in particular, indenyl, tetrahydroindene, fluorenyl and octahydronaphthalene.

Neo method of polymerization with a significant reduction in contamination of the reactor or without contamination during use of the catalyst on the carrier, in which alumoxane recorded on the media. According to the present invention, a good bulk densities for polymers based on the ethylene and copolymers are bulk density of at least 0.20 g/cm3preferably at least 0.25 g/cm3and even more preferably at least 0,30 g/cm3. It is likely that the degree of clogging of the reactor is connected with the number alumoxane arising from media under the conditions of polymerization, which leads to the fact that the active catalyst is a homogeneous phase dissolved in the diluent, in terms of justizorgane can give very fine particles of a polymer or polymer particles with poor morphology, which can stick to the metal parts or the static part of the reactor. Next is likely that the bulk density of the polymer is associated with the method of fixation alumoxane on the media and with the number of uncommitted alumoxane on the media, i.e., the amount of aluminum that can be extracted from the media toluene at 90oC. Fixation alumoxane on the media special treatment in accordance with the present invention leads to a significant reduction in the number alumoxane arising from media in which x in the polymerization mixture. It was found that these catalysts on the media can be used not only in obtaining the ethylene polymers and copolymers in the usual range of high density polyethylene (0,970 to 0,940 g/cm3methods suspension or gas-phase polymerization, but also copolymers with densities lower than 0,940 g/cm3to 0,880 g/cm3and even less, keeping a good space-density properties and preventing or substantially reducing the contamination of the reactor.

Component of the catalyst on the carrier of the present invention includes a carrier and alumoxane, where in General no more than 10% of the aluminum in the component of the catalyst on the carrier, extracted with toluene at 90oC for 1 hour using 10 ml of toluene, 1 g of the catalyst component on the carrier. Preferably, not more than 9% aluminum, located in the component of the catalyst on the carrier, could be extracted, and still more preferably not more than 8% aluminum could be extracted. It was found that if the amount of extractable compounds below these limits, the use of catalysts on a carrier, based on these components of the catalyst on the carrier, the resultant polymer is utilizator on the media with a known content of aluminium is added 10 ml of toluene and then heated the mixture up to 90oC in an inert atmosphere. A mixture of 1 hour mix well at this temperature. Then the suspension is filtered by applying a reduced pressure to accelerate the stages of filtration. The solid phase is twice washed with 3-5 ml of toluene to a temperature of 90oC per 1 g of the solid phase. The solid phase is then dried for 1 hour at 120oC, and then determine the content of aluminum in the solid phase. The difference between the initial content of aluminium and aluminium content after extraction divided by the initial aluminum content and multiplied by 100%, getting the amount of extractable aluminum.

The content of aluminium define suspending 0.5 g catalyst component on the carrier in 10 ml of hexane. The suspension is treated with 10 to 15 ml of 6 N. sulfuric acid, then add a known excess EDTA. Excess EDTA then octarepeat reverse titration of chloride of zinc.

At the level of 10% axtariram substances bulk density of the polymer obtained by polymerization using catalysts described here on the media (components), are very sensitive to small changes of the percentage of extractable aluminum. Due to the sensitivity of the bulk density of the polymer and limit pogressive test for distinguishing component of the catalyst on the carrier and catalyst on the carrier of the present invention, using the catalyst on the carrier for the polymerization of ethylene in a hydrocarbon solvent at 80oC and 15 bar, and determine the degree of clogging of the reactor and/or bulk density of the obtained ethylene polymer. The practical absence of clogging of the reactor, i.e. the polymer is practically not deposited on the walls of the reactor and the stirrer, and/or bulk density of at least 0.20 g/cm3and more preferably from 0.25 g/cm3characterize the developed components of the catalysts on the media and catalysts.

Suitable to this invention, the substrates may have a surface area defined by nitric parametria by BET method, of from 10 to 1000 m2/g, preferably from 100 to 600 m2/year Porosity media is mainly from 0.1 to 5 cm3/g, preferably from 0.1 to 3 cm3/g, even more preferably from 0.2 to 2 cm3/the Average particle size does not matter, but is usually from 1 to 200 microns.

Suitable carriers for catalysts on a carrier according to the present invention include porous rubbers such as styrene-divinylbenzene copolymers, solid inorganic oxides, such as kremnezem, aluminum oxide, magnesium oxide, titanium oxide, oxide torise silicon-magnesium or silicon aluminum. As carriers preferred are silica, aluminum oxide, mixed oxides of silicon and one or more of the 13 oxides of metals of group II. The most preferred silica. The silica may be granulated, agglomerated, powdered or other form. Suitable silica manufactured by Grace Davison (a division of W. R. Grace & Co.) under the brands of SD 3216.30, Davison Syloid 245, Davison 948 and Davison 952, and Degussa AG under the trademark Aerosil 812.

Before using them, if required, the media can be subjected to heat treatment and/or chemical treatment to reduce the moisture content or the content of hydroxyl substance carrier. Usually the preliminary heat treatment is carried out at a temperature of from 30 to 1000oC for from 10 minutes to 50 hours in an inert atmosphere or under reduced pressure.

Component of the catalyst on the carrier further includes alumoxane component. Alumoxane (also called alumination) is an oligomeric or polymeric oxycontintear aluminum containing chains of alternating atoms of aluminum and oxygen, and aluminum shall be borne by the Deputy, preferably alkyl group. The exact structure of alumoxane unknown, but it is usually assumed that h is SUB>m-AlR2for linear compounds, where R, independently of one another represent C1-C10-hydrocarbon, preferably alkyl or halide, a m is an integer from 1 to 50, preferably not less than 4. Alumoxanes are typically the reaction products of water with alkylamines, which in addition to the alkyl group may contain halide or alkoxygroup. The interaction of several different alkylaromatic compounds, such as, for example, trimethylaluminum, triiso-butylamine, with water gives the so-called mixed or modified alumoxane. Preferred alumoxane are methylalumoxane and methylalumoxane, modified with small amounts of other lower alkyl groups such as ISO-butyl. Alumoxane usually contain minor to significant amounts original alkylamino connection.

The method of producing alumoxane to the present invention it does not matter. Upon receipt by the reaction between water and alkylamines water can connect with alkylamines in various forms such as liquid, vapor or solid phase, for example in the form of water of crystallization. Private methods of obtaining compounds of the type alumoxane through to the deposits in U.S. Pat 4542199. In the private preferred implementation alkylamine contact with a regenerated aqueous substance, such as hydrated alumina, silica, or another substance. This is described in the patent EP N 338044.

Component of the catalyst on the carrier of the present invention usually contains from 15 to 40 wt.%, preferably from 25 to 40 wt.% aluminum from the General mass media and alumoxane. Predominant are the amounts of aluminum at least 15 wt.%, preferably from 20 wt.%, and most preferably from 25 wt. % because it allows precipitate on the carrier relatively large number of transition metal compounds and to obtain a relatively high activity. This improves the overall efficiency of the catalyst, particularly expressed through the media.

Component of the catalyst on the carrier itself or in the form of a suspension can be stored or transported in an inert environment or can be used for the production of catalyst on the carrier of the present invention.

According to another aspect of the present invention provides a catalyst on a carrier, including a component of the catalyst on the carrier of the present invention, and the connection perey or acyclic-linked anionic ligand, preferably cyclopentadienyls or substituted cyclopentadienyls particle. Suitable complexes are derivatives of any transition metal including lanthanides, but preferably of groups III, IV, V or lanthanides, being in a formal oxidation state of +2, +3 or +4. Preferred compounds include metal complexes containing from 1 to 3-linked anionic ligands, which may be cyclic or acyclic ligands associated delocalized-links. Examples of such related delocalized-bonded anionic ligands are paired or unpaired cyclic or acyclic dianiline group, allyl group, and arene groups. The term"associated" means that the ligand is associated with a transition metal connection. Each atom in the group with delocalized-links may be independently substituted by a radical selected from halogen, hydrocarbide, halogenerator or hidrocarbonetos metalloidal radical, where the metalloid is selected from group 14 of the Periodic table of the elements, CRC Press Inc., 1989. Included in the term "hydrocarbon" radicals preferably are C1-20normal, branched or cyclic alkyl, R is 7-20 aryl-substituted alkyl radicals. In addition, two or more such radicals may together form a closed ring or gidrirovannoe a closed ring. Suitable gidrokarbonatnye metalloorganic radicals include mono-, di - and tizanidine metalloorganic radicals of the elements of group 14, where each of hydrocarbonrich group consists of from 1 to 20 carbon atoms. Examples of suitable hydrocarbonoclastic metalloorganicheskikh radicals include trimethylsilyl, triethylsilyl, ethyldimethylamine, methyldiethylamine, triphenylene and trimethylgermyl.

Examples of suitable related delocalized-bonded anionic ligands include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindene, tetrahydrofluorene, octahydronaphthalene, pentadienyl, cyclohexadienyl, dihydroanthracene, hexahydrotriazine and decahydronapthalene, as well as their C1-10gidrokarbonatnye derivatives. Preferred anionic groups associated delocalized-links are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl, 2,3-dimethylindole, fluorenyl, 2-methylindenyl and 2-methyl-4-phenylindane.

Used the e cyclopentadienyls particles. Suitable metallocene for use in the present invention are or not containing bridge connection of mono-, di - and tricyclopentadiene or substituted cyclopentadienyls of transition metal compounds.

Suitable monosyllabically or mono(substituted) cyclopentadienyls derivatives of transition metals that do not contain bridge of communication, presents the General formula CpMXnwhere Cp is cyclopentadienyl or a derivative; M represents a transition metal III, IV or V of the group, having a formal oxidation state of 2, 3 or 4; X is independently from each other represent an anionic ligand (other than a cyclic, aromatic anionic ligand, linked-bond), X is specified to 50 atoms in addition to hydrogen atoms; and n represents the number that is one less than the formal oxidation state of M, is 1, 2 or 3, preferably 3. Examples of such ligands are hydrocarbon, hydrocarbonate, hydrogen, halogen, silyl, germyl, amide or siloxy, or two groups X together can form hydrocarbide (including hydrocarbide).

Suitable monosyllabically or mono(substituted cyclopentadienyls) connection="ptx2">

Examples of such complexes and methods for their preparation are set out in the application U.S. N 545403, filed July 3, 1990 (corresponding to EP-A-416815), U.S. Pat. USA 5374696 (corresponding to WO-93/19104), and U.S. Pat. USA 5055438, 5057475, 5096867, 5064802 and 5132380.

In more detail, the preferred monosyllabically or mono(substituted cyclopentadienyls) transition metal compounds containing bridging connection, correspond to the formula I

I

where M represents a metal from groups III to V, especially group IV, in particular titanium;

Cp*is substituted cyclopentadienyls group associated with Z' and status5related to M or such a group that contains from 1 to 4 substituents selected from hydrocarbide, Silla, hermila, halogen, hydrocarbonate, amino groups and mixtures thereof; these deputies have up to 20 atoms except hydrogen atoms, or, optionally, two such substituent (except halogen and amino groups) together form a closed ring Cp*.

Z' is a divalent Deputy, non-cyclic or acyclic anionic ligand; specified Z' includes boron or an element of group 14 of the Periodic table of elements, and optionally nitrogen, phosphorus, sulfur or oxygen; specified the ring.

X independently of one another are anionic ligands (non-cyclical-related group), having up to 50 atoms except hydrogen atoms; and

n is 1 or 2 depending on the valence of M.

In accordance with the preceding explanation, preferably M is a metal of group IV, especially titanium; n is 1 or 2, and X is a monovalent ligand containing up to 30 atoms in addition to hydrogen atoms, more preferably is C1-20hydrocarbon.

If n is 1, and a metal from groups III to V, especially group IV, is in the formal oxidation state of +3, preferably X is a stabilizing ligand.

The term "stabilizing ligand" means a ligand that stabilizes the complex metal through the following:

1) chelate connection with nitrogen, phosphorus, oxygen or sulfur or

2)3connection with resonance delocalized electronic system.

Examples of stabilizing ligands of type 1 include silyl, hydrocarbon, amide or was ligands, substituted by one or more aliphatic or aromatic ether, thioester, amino - or phosphinic groups, especially such amino - or phosphinic groups that are treatedpatients stabilizing ligands of type 1 are 2-dialkylaminomethyl or 2-(dialkylaminomethyl)phenyl group, containing from 1 to 4 carbon atoms in the alkyl group.

Examples of stabilizing ligands of type 2 include C3-10gidrolabilna group containing unsaturated ethylene fragment, such as allyl, 1-methylallyl, 2-methylallyl, 1,1-dimethylallyl or 1,2,3-trimethylsilyl.

More preferably, such a coordination metal complexes correspond to the formula II

< / BR>
R' independently from each other selected from hydrogen, hydrocarbide, Silla, hermila, cyano, halogen or combinations thereof having up to 20 atoms except hydrogen atoms, or two R' (except cyano or halo) together form their divalent derivative;

X independently from each other selected from hydride, halogen, alkyl, aryl, Silla, hermila, aryloxy, alkoxy, amide, siloxy and combinations thereof having up to 20 atoms except hydrogen atoms;

Y represents a divalent anionic ligand containing nitrogen, phosphorus, oxygen or sulfur and having up to 20 atoms except hydrogen atoms; the specified Y when bound to Z or M through these nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a closed ring; and

M is a metal of group IV, especially titanium;

Z is SiR2*, CR2*, SiRSUP>*,

GeR2*, BR*or BR2*where

R*independently from each other selected from hydrogen, hydrocarbide, Silla, halogenoalkane, halogenfree with 20 atoms except hydrogen and mixtures thereof, or two or more*from Z or R*Z together with Y form a closed ring; and

n is 1 or 2.

Even more preferably, when Y is-O-, -S-, -NR*-, -PR*-. Most preferably, when Y is nitrogen or fosforsoderzhashchie group corresponding to the formula - N(R') -, or-P(R')-, where R' is as previously described, is amide or was the group.

The most preferred coordination metal complexes correspond to the formula III

< / BR>
where M is titanium;

R' independently from each other selected from hydrogen, Silla, hydrocarbide or combinations thereof having up to 10 carbon atoms or silicon, or two R' substituted cyclopentadienyls fragment connected together;

X independently from each other selected from hydride, halogen, alkyl, aryl, aryloxy having up to 10 carbon atoms;

m is 1 or 2; or

n is 1 or 2.

Examples of the above most preferred coordination compounds of the metal, where R' in amidon, the phenyl or cyclododecyl; (ER'2)mis dimethylsilanol or 1,2-ethylene; R' cyclic-linked group independently of one another are hydrogen, stands, ethyl, propylene, bootrom, Pentium, hexyl, norbornyl, benzyl or phenyl, or two R' are connected, forming indenyl, tetrahydroindene, fluorenyl or octahydronaphthalene, and X is chlorine, bromine, iodine, stands, ethyl, propylene, bootrom, Pentium, hexyl, norbornyl, benzyl or phenyl.

Particularly preferred compounds are (tert-butylamino)-(tetramethyl -5-cyclopentadienyl)-1,2 - tendercompetition, (tert-butylamide)(tetramethyl-5-cyclopentadienyl)-1,2-atandardization, (tert-butylamide)(tetramethyl-5-cyclopentadienyl)dimethylbenzonitrile, tert-butylamide)(tetramethyl-5-cyclopentadienyl)dimethylsilyldiethylamine (methylamide)(tetramethyl-5-cyclopentadienyl)dimethylbenzonitrile (methylamide)(tetramethyl-5-cyclopentadienyl)dimethylsilyldiethylamine (phenylamino)(tetramethyl-5-cyclopentadienyl)dimethylbenzonitrile (phenylamino)(tetramethyl- -5-cyclopentadienyl)dimethylsilyldiethylamine (benzylamino)(tetramethyl - milliardenpleite, (tert-butylamide) (5-cyclopentadienyl)-1,2-tendercompetition, (tert-butylamide)(5-cyclopentadienyl)-1,2-atandardization, (tert-butylamide) (5-cyclopentadienyl)-dimethylbenzonitrile, (tert-butylamide) (5-cyclopentadienyl)-dimethylsilyldiethylamine (methylamide) (5-cyclopentadienyl)-dimethylbenzonitrile, (tert-butylamide) (5-cyclopentadienyl)-dimethylsilyldiethylamine, (tert-butylamino)interdimensionality and appropriate coordination complexes of zirconium and hafnium.

Compounds of transition metals, where transition metals are in the formal oxidation state of +2, and methods for their preparation is described in detail in WO 9500526 that corresponds to the application of the U.S. N 241523, filed may 12, 1994. Suitable complexes include compounds containing one and only one cyclic delocalized, anionic-linked group, correspond to the formula IV

< / BR>
where M is titanium or zirconium in the formal oxidation state of +2.

L is a group containing a cyclic delocalized anionic system, which is associated with group M, and associated with a z group.

Z is the particle associated with M is sulfur or oxygen; said particle has up to 60 atoms except hydrogen atoms; and

X*is neutral paired or unpaired-diene, optionally substituted with one or more hydratability groups; X is specified to 40 carbon atoms and forms a complex with M

Preferred transition metal compounds of formula IV include compounds where Z, M and X*such as previously described; and L is C5H4group attached to Z, and position5attached to M, or this5-joined the group, having from 1 to 4 substituents, independently selected from hydrocarbide, Silla, hermila, halogen, cyano, and combinations thereof; specified substituent has up to 20 atoms in addition to hydrogen atoms, and optionally two such substituent (except cyano or halo) together form a closed ring L.

More preferable compounds of the transition metal (+2) according to the present invention correspond to the formula V

< / BR>
where R' independently from each other selected from hydrogen, hydrocarbide, Silla, hermila, halogen, cyano or combinations thereof; these R' have up to 20 atoms in addition to hydrogen atoms, and optionally, two R' (where R' is hydrogen, cyano or galerileri derived with the formation of a closed ring;

X*is neutral4-linked group having up to 30 atoms in addition to hydrogen atoms, which forms a complex with M;

Y is-O-, -S-, -NR*-, -PR*-;

M is titanium or zirconium in the formal oxidation state of +2;

Z*is SiR2*, CR2*, SiR2*/SiR2*, CR2*/CR2*, CR*=CR*, CR2*SiR2*or GeR2*where

R*independently from each other selected from hydrogen, hydrocarbide, Silla, halogenoalkane, halogenfree and their combinations; the specified R*has up to 20 atoms except hydrogen, and optionally two of R*from the Z*(where R*is not hydrogen), or R*from the Z*and R*from Y form a ring.

Preferably R', independently of one another, are hydrogen, hydrocarbon, silicom or halogen, and combinations thereof; these R' have up to 10 atoms in addition to hydrogen atoms, and optionally, two R' (where R' is hydrogen or halogen) together are divalent derivative; most preferably, when R' is hydrogen, stands, ethyl, propylene, bootrom, Pentium, hexyl (including all podhodjashee, thus the whole group CsR'4is, for example, indenolol, tetrahydroindene, fluorenyl, tetrahydrofluorene or octahydronaphthalene.

Further, it is preferable that at least one of R' or R*was the donor particle. The term "electrondensity" means that the particle is more electron-donating than hydrogen. Thus, most preferably, Y was nitrogen - or fosforsoderzhashchie group corresponding to the formula-N(R") -, or-P(R")-, where R" is C1-10hydrocarbon.

Examples of suitable groups X*include: s-TRANS41,4-diphenyl-1,3-butadiene, s-TRANS-4-3-methyl-1,3-pentadiene, s-TRANS-41,4-dibenzyl-1,3-butadiene, s-TRANS-4-2,4-hexadiene, s-TRANS-4-1,3-pentadiene, s-TRANS-4-1,4-ditolyl-1,3-butadiene, s-CIS-41,4-diphenyl-1,3-butadiene, s-CIS-4-3-methyl-1,3-pentadiene, s-CIS-41,4-dibenzyl-1,3-butadiene, s-CIS-4-2,4-hexadiene, s-CIS-4-1,3-pentadiene, s-CIS-4-1,4-ditolyl-1,3-butadiene, s-CIS-4-1,4-bis(trimethylsilyl)-1,3-butadiene; these s-CIS-diene form a complex with the metal as defined here.

The most preferred compounds of transition metals (+2) are R")-, a R' independently from each other selected from hydrogen, Silla, hydrocarbide and their combinations; these R' has up to 10 carbon atoms or silicon, or two R' on the substituted cyclopentadienyls group (where R' is not hydrogen) together form their divalent derivative that is attached adjacent to the provisions of cyclopentadienyls ring;

R" is C1-10hydrocarbon;

R"' independently of one another are hydrogen or C1-10hydrocarbon;

m is 1 or 2.

Examples of the metal complexes in accordance with the present invention include compounds where R" is stands, ethyl, propylene, bootrom, Pentium, hexyl (including all previous relevant isomers), cyclododecyl, norbornyl, benzyl or phenyl; (ER"'2)mis dimethylsilanol or ethandiol; cyclic delocalized p-knit group is cyclopentadienyl, tetramethylcyclopentadienyl, indenolol, tetrahydroindene, fluorenyl, tetrahydrofluorene or octahydronaphthalene.

Suitable bis-cyclopentadienyls or substituted cyclopentadienyls of transition metal compounds include compounds containing bridging group linking aniline or bis(substituted cyclopentadienyls) derivative of the transition metal, does not contain a bridge of communication, presents the General formula Cp2MXnwhere Cp is associated cyclopentadienyls group or associated substituted cyclopentadienyls group, and M and X are defined in formula II and n' is 1 or 2 and by 2 less than the formal oxidation state of M, Preferably n' is 2. Examples of bis-cyclopentadienyls derivatives of the transition metal that does not contain bridging ties are biscyclopentadienyl, biscyclopentadienyl, bis(methylcyclopentadienyl)dimethylzirconium, bis(n-butylcyclopentadienyl)dimethylzirconium, bis(t-butylcyclopentadienyl) dimethylzirconium, bis(pentamethylcyclopentadienyl)dimethylzirconium, bis(indenyl)dibenzalacetone, bis(fluorenyl)dimethylzirconium, bis(pentamethylcyclopentadienyl)bis[2-(N, N-dimethylamino)benzyl] the zirconium and the corresponding derivatives of titanium and hafnium.

Preferred bridging groups are groups conforming to the formula (ER"2)xwhere E is carbon or silicon, R" independently of one another are hydrogen or a group selected from Silla, hydrocarbide and their combinations; the specified R ' has up to 30 carbon atoms or silicon, and x is from 1 to 8. PR is Karami ligands to bridge connections, containing twin-linked groups are: (dimethylsilane bis-cyclopentadienyl), (dimethylsilane-bis-methylcyclopentadienyl), (dimethylsilane-bis - ethylcyclopentadienyl), (dimethylsilane-bis-tert-butylcyclopentadienyl), (dimethylsilane-bis-tetramethylcyclopentadienyl), (dimethylsilane-bis-indenyl), (dimethylsilane - bis-tetrahydroindene), (dimethylsilane-bis-fluorenyl), (dimethylsilane-bis-tetrahydro-fluorenyl), (dimethylsilane-bis-2-methyl-4-phenylindane), (dimethylsilane-bis-2-methylindenyl), (dimethylallyl-cyclopentadienylmagnesium), (1,1,2,2-Tetra-methyl-1,2-diziler bis-cyclopentadienyl), (1,2-bis(cyclopentadienyl)ethane and (ISO - propylidene-cyclopentadienyl-fluorenyl).

Examples of previous biscyclopentadienyl or bis(substituted cyclopentadienyls) complexes are compounds corresponding to formula VI:

< / BR>
where M, X, E, R', m and n are the same as defined for formula III. Two Deputy X together can form a neutral-linked conjugated diene having from 4 to 30 atoms in addition to hydrogen atoms, forming a complex with M, where M being preferably zirconium or hafnium, is in the formal oxidation state of +2.

The foregoing metal complexes redoctane, to the complex had a Cs-symmetry or possessed chiral hard stereostructures. Examples of compounds of the first type are compounds with different delocalized systems-relations, such as one cyclopentadienyls group and one fluoroaniline group. Similar systems based on Ti(IV) or Zr(IV) have been described upon receipt syndiotactic olefin polymers in Ewen et al., J. Am. Chem. Soc. Vol. 110, pp. 6255-6256 (1980). Examples of chiral structures include bis-Ingenierie complexes. Similar systems based on Ti(IV) or Zr(IV) have been described upon receipt isotactic olefin polymers in Wild et al., J. Were Obtained. Chem. Vol. 232, pp. 233-47 (1982).

Examples of complexes of the formula IV are: (dimethylsilane bis - cyclopentadienyl)dimethylzirconium, (dimethylsilane-bis - tetramethylcyclopentadienyl)dimethylsilane, (dimethylsilane-bis - tert-butylcyclopentadienyl)-diphenylsilane, (dimethylsilane-bis - tetramethylcyclopentadienyl)dibenzyl-zirconium (dimethylsilane-bis - indenyl)bis(2-dimethylaminobenzoyl)zirconium, (ISO-propylidene - cyclopentadienyl-fluorenyl)dimethylzirconium, [2,2'-biphenyldiol-bis(3,4-dimethyl-1-cyclopentadienyl)] debenzylation, [6,6-dimethyl-2,2'-biphenyl bis(3,4-dimethyl-1-cyclopentadienyl)] dimethylzirconium and sootvetstvennye derivative of the transition metal include connection containing bridging group linking the two cyclopentadienyls groups or compounds without such bridging groups.

Suitable tricyclopentadiene derivative of the transition metal represented by the General formula Cp3MXnwhere Cp, M and X are defined as before, and n is 3 less than the formal oxidation state of M, and is 0 or 1, preferably equal to 1. Preferred ligands X are hydrocarbon, hydrocarbonate) hydride, halogen, silyl, germyl, amido, siloxy.

Preferably the compound of the transition metal is monosyllabically connection with a bridge connection of a transition metal of group IV or biscyclopentadienyl connection with a bridge connection of a transition metal of group IV, more preferably monosyllabically compound of the transition metal, in particular in this connection, where the metal is titanium.

Other compounds used in the preparation of catalytic compositions in accordance with the present invention, particularly compounds containing other metals of group IV, undoubtedly well-known experts in this field.

Usually the molar ratio of aluminum atoms (from alumoxanes K5 1000, and more preferably from 50 to 500. If too small ratios of the catalyst on the carrier is not particularly active, while when too high ratios of catalyst becomes economically less advantageous because of the relatively high cost associated with the use of large quantities of alumoxane.

The amount of coupling of the transition metal in the catalyst on the carrier according to the present invention is not matter but usually varies from 1 to 1000 micromoles of compounds of the transition metal per gram of the carrier. Preferably the catalyst on the carrier contains from 1 to 250 micromoles of compounds of the transition metal per gram of the carrier. It was found that increasing the aluminum content in the media leads to catalysts with higher efficiency, counting on the transition metal, compared to catalysts with a lower content of aluminum with the same ratio of aluminum/transition metal. These media components with a higher aluminum content also lead to catalysts with higher efficiency, considering both the aluminum and the media.

The catalyst on the carrier of the present invention can be used by itself or in forpo the

Component of the catalyst on the carrier according to the present invention can be obtained by heating the media containing alumoxane, in an inert atmosphere for a time and at a temperature sufficient to commit alumoxane on the media.

Media containing alumoxane can be obtained compound in the solvent alumoxane with media containing from 1 to 20 wt.% water, preferably from 0 to not more than 6 wt.% water from the total mass of media and water. Media containing no water, give good results in relation to the catalytic properties of the catalyst on the carrier. In addition, it was found that the media containing relatively small amounts of water can easily be used in this way. Water-containing medium when the connection under the same conditions with the same number alumoxane in this way give a catalyst component on the carrier, with a slightly higher content of aluminum than practically anhydrous media. It is likely that water reacts with residual quantities alkylamine present in alumoxane, turning alkylamine additional alumoxane. In addition, the advantage is that less alkylamine tertiarytype, media containing alumoxane can be obtained compound in the solvent media containing 5 to 30 wt.% water, preferably from 6 to 20 wt.% the water of the total weight of the carrier and water, with the compound of the formula R ' nAlX"3-nwhere R" independently from each other are hydratability radicals, X is halogen or hydrocarbon, and n*is an integer from 1 to 3. Preferably and n*equal to 3. If alumoxane obtained in situ by the interaction of the compounds of formula Rn*AlX"3-n*with water, the molar ratio of Rn*AlX"3-n*and water is usually from 10:1 to 1:1, preferably from 5:1 to 1:1.

Media is added to alumoxane or the compound of the formula R ' n*AlX"3-n*preferably dissolved in the solvent, most preferably in a hydrocarbon solvent, or a solution alumoxane or compounds of the formula R ' n*AlX"3-n*added to the media. The media can be used by itself or in suspension in a hydrocarbon solvent. Can be used as aliphatic and aromatic hydrocarbons. Suitable aliphatic hydrocarbons include, for example, pentane, ISO-pentane, hexane, heptane, octane, ISO-octane, nonan, the examples of aromatic hydrocarbons are benzene, toluene, xylenes, and other alkyl - or halogen-substituted aromatic compounds. Most preferably, when the solvent is an aromatic hydrocarbon, especially toluene. Suitable concentrations of particulate media in the hydrocarbon environment vary from 0.1 to 15, preferably from 0.5 to 10, more preferably from 1 to 7 wt.%. The time of contact and temperature are not important. Preferred temperatures from 0 to 60oC, more preferably from 10 to 40oC. the Time of contact varies from 15 minutes to 40 hours, preferably from 1 to 20 hours.

Before stage heat containing alumoxane media remove the diluent or solvent to obtain a free flowing powder. Preferably this is done using a method that allows you to remove only the liquid and leaves the aluminum compounds in the solid phase, such as heat, pressure drop, evaporation or a combination of these methods.

Stage heating And subsequent optional stage leaching B is carried out in such a way that fixed the majority (more than 90 wt.%) alumoxane remaining in the component of the catalyst on the carrier. At the stage of heating alumoxane piccirelli degree removed, and forms a component of the catalyst on the carrier of the present invention. The highest temperature of heat treatment is preferably below the temperature at which the material of the carrier begins to aglomerirovanie and form clumps that are difficult to be atomized, and below the temperature of decomposition alumoxane. If before heat treatment type metallocene compound, as it will be explained here, the temperature of heating should be below the temperature of decomposition of the metallocene compound. Media containing alumoxane, in the form of a free flowing powder is preferably subjected to heat treatment at a temperature of at least 75oC, preferably at a temperature of at least 85oC, more preferably at a temperature of at least 100oC to 250oC, more preferably at a temperature of up to 200oC for from 15 minutes to 72 hours, preferably up to 24 hours. More preferably, heat treatment is performed at a temperature of from 160 to 200oC for from 30 minutes to 4 hours. Good results were obtained when heated for 8 hours at 100oC, as and when heated for 2 hours at 175oC. using predvaritelny result. It is noted that the longer the duration of the heat treatment, the greater the number alumoxane recorded on the media. The heat treatment is carried out under reduced pressure or in an inert atmosphere, such as gaseous nitrogen, but preferably under reduced pressure. Depending on the conditions under heating alumoxane can be recorded on the carrier in such a high degree that stage washing can be omitted.

In optional stage of leaching, B the number of leaching and the amount of solvent used is such that provide significant removal of uncommitted alumoxane when receiving component of the catalyst on the carrier of the present invention. The washing conditions should be such that metafictionality alumoxane would have dissolved in the washing solvent. Containing alumoxane media, already subjected to heat treatment, preferably washed from 1 to 5 times an aromatic hydrocarbon solvent at a temperature of from 0 to 110oC. More preferably the temperature varies from 20 to 100oC. Preferred examples of aromatic solvents include toluene, benzene and xylenes. More preferably aromatic oglevee remove dissolved alumoxane, such as filtration or decantation. Preferably the washing solvent is removed with the formation of a free flowing powder component of the catalyst on the carrier.

Stage leaching can be successfully carried out at the reflux distilled leaching solvent. Conducting stage of leaching under conditions of reflux distilled allows you to control the parameters of the distribution of particle sizes, preferably receiving a distribution similar to the distribution in the source media, and it was found that the catalyst on the carrier thus has a higher polymerization activity. In General, the catalyst on the carrier after heating stage is suspended in an aromatic hydrocarbon, and the suspension is refluxed or heated to the boiling point of the aromatic hydrocarbon. The suspension is maintained under these conditions for from 5 minutes to 72 hours. All agglomerated particles, which may be formed during the stage of heating, it is necessary to deagglomerate or dispersing under leaching conditions boiling under reflux. The longer is boiling under reflux, the better the achieved dispersion. The concentration of the component katal is preferably from 10 to 250 g per liter. Preferred examples of aromatic hydrocarbons include toluene, benzene and xylenes. More preferably, the aromatic hydrocarbon is toluene. While boiling under reflux may be stirring.

Component of the catalyst on the carrier of the present invention after the above stages of washing or boiling under reflux is preferably subjected to dispersion before merging component of the catalyst on the carrier with the compound of the transition metal. It was found that this increases the catalytic activity of the final catalyst on the carrier. In General, as the dispersion medium used aliphatic, cycloaliphatic or aromatic hydrocarbon. Suitable examples are aliphatic hydrocarbons having from 6 to 20 carbon atoms, preferably from 6 to 10 carbon atoms, or a mixture thereof. Temperature does not matter, but is appropriate interval from 0 to 50oC. Duration from 5 minutes to 72 hours. The upper limit does not matter, but is determined by practical considerations.

The transition metal compound is preferably added after the heating stage is whether the transition metal compound added before any of these stages, you should take measures to ensure not to put it too high temperature, which may cause degradation or loss of activity. Mainly with the unity of the transition metal type stage after washing to prevent leaching of the transition metal together with alumoxanes of the media.

The transition metal is in contact with the medium containing alumoxane, and preferably with a component of the catalyst on the carrier of the present invention in the diluent, preferably in those conditions in which the transition metal compound is soluble. Suitable diluents include aliphatic and aromatic hydrocarbons, preferably aliphatic hydrocarbons, such as hexane. Metallocen preferably added to the suspension media, mainly dissolved in the same solvent in which the suspended media. In General, the media containing alumoxane, suspendered in the diluent at a concentration of from 1 to 20, preferably from 2 to 10 wt.%. The time of contact and temperature are not important. The preferred temperature is from 10 to 60oC, more reverent before the temperature from 20 to 45oC. the Time of contact of metallocene. This can be done by any suitable method, such as application of heat and/or pressure drop, evaporation, filtration or decantation or a combination thereof. If you change the heating, the temperature should not exceed the decomposition temperature of metallocene.

It may be useful to polimerizuet olefin in the presence of catalyst on the carrier to obtain terpolymerization catalyst on the carrier.

In the most preferred implementation of the method of producing catalyst on the carrier includes

heating the silica carrier containing methylalumoxane, to a temperature of from 75 to 250oC in an inert atmosphere, preferably under reduced pressure;

optional subsequent single or multiple washing the toluene product stage heating;

the selection conditions of the stages of heating and washing, thus, to obtain a catalyst component on the carrier, which at one-hour extraction with toluene at 90oC using 1 g of the component of catalyst per 10 g of toluene is extracted no more than 9% of the aluminum present in the catalyst component on the carrier; and

the addition of after-stage heating and optional stilloperating) compounds of transition metals of group IV of the bridge with the link provided after adding the compound of the transition metal, the resulting product is not exposed to temperatures equal to or greater than its decomposition temperature.

Preferably, the thus obtained catalyst contains from 20 to 40 wt.% aluminum to the total weight of the carrier and alumoxane. Mainly the molar ratio of atoms of aluminum and the transition metal in the thus obtained catalyst on the carrier is in the range from 25 to 1000. Preferably, the thus obtained catalyst on the carrier contains from 0.1 to 1000 micromoles of compounds of the transition metal per gram of the carrier.

Thus obtained catalyst on the carrier can be used as such without isolation or purification, but preferably initially provided in the form of free flowing particles. The selected catalyst may be stored in an inert atmosphere for a long period of time, for example from one to several months. Before use the catalyst on the carrier can be easily re-suspended in the diluent, preferably a hydrocarbon. This catalyst on the carrier does not require additional activators or acetalization.

In other aspach monomers under conditions polyaddition contact with the catalyst on the carrier of the present invention.

Suitable monomers for polyaddition include ethylene unsaturated monomers, acetylenic compounds, conjugated or unpaired dieny, the polyene and carbon monoxide. Preferred monomers include, for example, alpha-olefins having from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8 carbon atoms, and combinations of two or more of such alpha-olefins. Particularly suitable alpha-olefins are, for example, ethylene, propylene, 1-butene, 1-penten, 4-methylpentene-1, 1-hepten, 1-octene, 1-none, 1-mission 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecane or combinations thereof. Preferably, the alpha-olefins are ethylene, propylene, 1-butene, 4-methylpentene-1, 1-hexene, 1-octene and combinations of ethylene and/or propylene with one or more other alpha-olefins. Other preferred monomers include styrene, halogen - or alkyl substituted styrene, vinyl chloride, Acrylonitrile, methyl acrylate, methyl methacrylate, Tetra - veratile, Methacrylonitrile, vinylidenechloride, vinylcyclopentane, 1,4-hexadiene and 1.7-octadiene. Suitable monomers for polyaddition also include any mixture of the above monomers.

The catalyst on the carrier can be obtained in situ polymerization in the th component. Component of the catalyst on the carrier and the catalyst on the carrier of the present invention can successfully be used in the methods of polymerization under high pressure, solution, suspension or in the gas phase. Polymerization under high pressure is usually conducted at a temperature of from 100 to 400oC and pressures above 500 bar. In the suspension method is commonly used inert hydrocarbon diluent and temperature from 20 to 115oC, preferably from 60 to 105oC. Method of polymerization in solution is implemented at temperatures from the temperature at which the formed polymer is soluble in an inert solvent, up to 275oC. In General, the solubility of the polymer depends on the density. For ethylene copolymers having a density of about 0,86 g/cm3polymerization in solution is achieved at a temperature of about 60oC. Preferably the temperature range for polymerization in solution ranges from 75 to 260oC, more preferably from 80 to 170oC. Usually as inert solvents are hydrocarbons, particularly aliphatic hydrocarbons. The polymerization in suspension and in solution is usually carried out at a pressure from 1 to 100 bar. Normal working conditions Asiana method is commonly used pressure from atmospheric to 100 bar. Typical gas-phase methods of polymerization are described in U.S. Pat. USA 4588790, 4543399, 5352749, 5405922 and the application of the U.S. N 122582, filed September 17, 1993 (corresponding to WO 9507942).

Preferably for use in gas-phase polymerization method, the carrier has an average particle diameter of 20 to 200 μm, more preferably from 30 to 150 μm and most preferably from 35 to 100 μm. Preferably when used in suspension polymerization method, the carrier has an average particle diameter of 1 to 200 μm, more preferably from 5 to 100 μm and most preferably from 20 to 80 μm. Preferably, when used in the method of polymerization in solution or polymerization under high pressure carrier has an average particle diameter of 1 to 40 μm, more preferably from 2 to 30 μm and most preferably from 3 to 20 μm.

When used in a slurry or gas-phase polymerization method, the catalyst of the present invention is able to give not only the ethylene copolymers with a density normal high density polyethylene in the range from 0,970 to 0,940 g/cm3but, unexpectedly, also able to give copolymers having a significantly lower density. Copolymers with densities below 0,940 g/cm

In the polymerization method of the present invention can be used absorbers impurities, which serve to protect the catalyst on the carrier from the catalytic poisons, such as water, oxygen and polar compounds. In General, these sinks can be used in amounts that depend on the impurity content, and are typically added in the download monomers or solvent, or in the reactor. Typical absorbents include trialkylaluminium or compounds of boron and alumoxanes.

In the present method, the polymerization can also be used by the agents to control molecular weight, such as hydrogen or other chain transfer agents.

In describing the invention, the following examples are provided as further illustration and not serve its limitations. All of the shares or interest are mass, unless otherwise specified.

Examples

The examples use the following media: granular silica production Grace GmbH brand SD 3216.30; spherical agglomerated silica production Gr is ugogo is not specified, used silica was heated in a vacuum to 250oC for 3 hours to a final moisture content, practically equal to 0, defined scanning calorimetry. If you are using water-containing silica, it is used in the form in which it is supplied without preliminary heat treatment.

Alumoxane is used in the form of 10 wt.%-aqueous solution methylalumoxane (MAO) manufactured by Witco GmbH in toluene. Metallocene used as 0.0714 M solution of {(tert-butylamide)(tetramethyl -5- cyclopentadienyl)(dimethyl)silane} of dimethylsilane (hereinafter MCpTi) in ISOPARTME (a trademark of Exxon Chemical Company).

Bulk density of the obtained polymers was determined in accordance with ASTM 1895. The aluminium content in the media was determined by treatment with sulfuric acid, followed by EDTA titration and back-titration of chloride of zinc.

All experiments were conducted in an atmosphere of nitrogen, unless otherwise specified.

Example 1

In a flask with a capacity of 1000 ml load 11.1 g of silica SD 3216.30, add 300 g of a solution of MAO and the mixture is stirred for 16 hours. After that, the solvent is removed under reduced pressure at 20oC. Obtain 38 g of a free flowing powder containing the 2 hours under reduced pressure. After this processing determine the aluminum content in each sample, and then each sample is suspended in 100 ml of toluene, and the mixture is stirred for 1 h, the media was washed with 2 portions of 50 ml of fresh toluene and dried in vacuum at 120oC for 1 hour. The results of determination of aluminum are collected in table 1.

The above procedure was repeated with 12.1 g of silica and 327 g of a solution of MAO. Received 42 g of free flowing powder with aluminium content of 31.3%. This sample was divided into 4 equal portions and each was heated as described above, and then subjected to washing with toluene, using toluene to a temperature of 90oC. the Results are summarized in table 2.

These examples are for long-term heat treatments show that the increase in the temperature of the heat treatment increases the number alumoxane, zafiksirovalos on the silica. Rinse with toluene temperature 90oC leads to an increase in the percentage of uncommitted deleted aluminum compared to washing with toluene at room temperature for the same duration of washing.

Example 2

In a flask with a capacity of 250 ml upload 6.2 g of silica SD 3216.30, add 168 g of a solution of MAO and the mixture is stirred for 16 hours. Pic 16 hours at 20oC to obtain a free flowing powder. The mass of the solid phase is equal to 22.1 g, and the aluminium content of 26.8%.

Example 3

The method of example 2 is repeated, using 3 g of silica and 56,6 g of a solution of MAO. Obtain 7.6 g of free flowing powder with aluminium content of 26.1%. In 50 ml of toluene at 20oC suspended and 5.2 g of this carrier and the mixture is stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 20 ml of fresh toluene, and then dried in vacuum at 20oC for 1 hour. Mass is 3.0 g, aluminium content of 18.2%.

Example 4

The method of example 2 is repeated, using 3 g of silica and 75.6 g of a solution of MAO with obtaining free flowing powder. This powder is heated in vacuum at 100oC for 2 hours. Mass is equal to 8.4 g, the content of aluminum 29,0%. In 50 ml of toluene at 20oC suspended and 5.2 g of this carrier, and the mixture is stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 20 ml of fresh toluene, and then dried in vacuum at 20oC for 1 hour. Mass is equal to 2.2 g, the aluminum content of 17.3%.

Example 5

The method of example 2 is repeated, using 3 g of silica and 56,6 g of a solution of MAO with obtaining free flowing powder. The powder is heated in vacuum for 2 h the and 2 again, using flask with a capacity of 1000 ml, 12.1 g of silica and 327 g of a solution of MAO with obtaining free flowing powder. Then heated in a vacuum for 2 hours at 175oC 9.5 g of this powder. Certain aluminium content of 30.7%. In 40 ml of hexane at 20oC suspended 2.7 g of this carrier, and the mixture is stirred for 4 hours. The mixture is filtered, and the carrier was washed with 2 portions of 30 ml of fresh hexane, and then dried in vacuum at 20oC for 1 hour. Weight is 2.4 grams aluminum content of 30.4%.

Example 7

Continue the method of example 2. This powder is heated in vacuum for 2 hours at 150oC. the Mass is equal to 7.25 g, the aluminum content of 26.6%. In 40 ml of toluene at 20oC suspended 3 g of this carrier, and the mixture is stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 10 ml of fresh toluene, and then dried in vacuum at 20oC for 1 hour. Weight is 2.4 grams aluminum content of 24.1 per cent.

Example 8

The method of example 2 is repeated, using 3 g of silica and 75.5 g of a solution of MAO with obtaining free flowing powder. This powder is heated in vacuum at 150oC for 2 hours. Mass is equal to 8.4 g, the aluminum content of 29.8 per cent. In 40 ml of toluene at 20oC suspended 5 g of this carrier, and the mixture pregame at 20oC for 1 hour. Weight of 4.5 g, aluminium content of 28.9%.

Example 9

The method of example 2 is repeated, using a flask with a capacity of 1000 ml, and 9.1 g of silica and 246 g of a solution of MAO with obtaining free flowing powder. This powder is then heated in vacuum for 2 hours at 150oC. the Mass is equal to 29.0 g, the aluminum content of 29.6%. This carrier is suspended in 300 ml of toluene at 20oC, and the mixture is stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 100 ml of fresh toluene, and then dried in vacuum at 20oC for 1 hour. Mass is equal to 24.3 g, the aluminum content of 28.5%.

Example 10

The method of example 2 is repeated using 5 g of silica and 101 g of a solution of MAO with obtaining free flowing powder. This powder is heated in vacuum at 175oC for 2 hours. The aluminium content in this material is of 28.8%. In 130 ml of toluene, re-suspended 12.8 g of this powder, and the mixture is heated to 90oC and stirred for 1 hour. The mixture is filtered and the resulting solid phase was washed with 2 portions of 50 ml of fresh toluene at 90oC. the Medium is then dried in vacuum at 120oC for 1 hour. Obtain 10.4 g of the carrier with aluminium content of 26.3%.

Example 11

The way of Primak in vacuum heated at 175 for 2 hours. The aluminium content in the material is equal to 17.2%. In 150 ml of toluene, re-suspended 15.6 g of this powder, and the mixture is heated to 90oC and stirred for 1 hour. The mixture is filtered and the resulting solid phase was washed with 2 portions of 50 ml of fresh toluene at 90oC. the Medium is then dried in vacuum at 120oC for 1 hour. Get 13,0 g media with aluminium content of 16.3%.

Example 12

The method of example 2 is repeated using 5 g of silica SD 3216.30 with a moisture content of 2.8% and 101 g of a solution of MAO with obtaining free flowing powder. This powder is heated in vacuum at 175oC for 2 hours. The aluminium content in the material is equal to 29.4%. In 130 ml of toluene, re-suspended 13 g of this powder, and the mixture is heated to 90oC and stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 50 ml of fresh toluene at 90oC. the Carrier is dried in vacuum at 120oC for 1 hour. Get 11.5g media, a content of aluminum 29,0%.

Example 13

The method of example 2 is repeated, using a flask with a capacity of 1000 ml, 9 g of SYLOPOL 2212 and 243 g of a solution of MAO with obtaining free flowing powder. This powder is then heated in vacuum for 2 hours at 150oC. the Mass is equal to 29.3 g, the content of the aluminum carrier is washed with 2 portions of 100 ml of fresh toluene, then dried in vacuum at 120oC for 1 hour. The equal weight of 25.9 g, the aluminum content of 29.3%.

Example 14

The method of example 2 is repeated, using a flask with a capacity of 1000 ml, and 9.1 g of silica and 246 g of a solution of MAO with obtaining free flowing powder. This powder is then heated in vacuum for 2 hours at 175oC. Mass is equal 30,8 g, the aluminum content of 30.0%. This carrier is suspended in 300 ml of toluene at 20oC, and the mixture is stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 100 ml of fresh toluene, and then dried in vacuum at 120oC for 1 hour. Mass are 27.1 g, the content of aluminum 29,0%.

Example 15

The method of example 2 is repeated, using a 5.1 g of silica and 101 g of a solution of MAO with obtaining free flowing powder. In vacuum heated at 100oC within 2 hours of 6.8 g of this powder. The aluminium content in the material is equal to 17.2%. The carrier is suspended in 100 ml of toluene, and the mixture is heated to 90oC and stirred for 1 hour. The mixture is filtered and the resulting solid phase was washed with 2 portions of 50 ml of fresh toluene (90oC) and dried in vacuum at 100oC for 1 hour. Mass is 3.0 g, aluminium content of 16.6%.

Example 16

Way of example the La in the 90oC suspended 6.8 g of this powder and stirred for 1 hour. The mixture is filtered and the resulting solid phase was washed with 2 portions of 50 ml of fresh toluene (90oC) and dried in vacuum at 100oC for 1 hour. Mass is 3.0 g, aluminium content of 13.4%.

Example 17

The method of example 2 is repeated using 5 g of silica SD 3216.30 with a moisture content of 2.8% and 101 g of a solution of MAO with obtaining free flowing powder. In 100 ml of toluene at 90oC suspended 6 g of this powder, and the mixture is stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 50 ml of fresh toluene (90oC) and dried in vacuum at 20oC for 1 hour. Mass is equal to 2.9 g of the carrier, the aluminum content of 16.4%.

Example 18

The method of example 2 is repeated using 5 g of silica SD 3216.30 with a moisture content of 2.8% and 101 g of a solution of MAO with obtaining free flowing powder. This powder is heated at 100oC for 2 hours. In 100 ml of toluene suspended 6 g of this powder, and the mixture is heated at 90oC and stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 50 ml of fresh toluene (90oC) and then dried in vacuum at 20oC for 1 hour. Obtain 3.8 g of the carrier, the aluminum content of 22.2%.

Preliator on the media, obtained in examples 2 to 18, according to the following method.

Typically, 1 g of the carrier is suspended in 20 ml of hexane, and the mixture is stirred for 30 minutes. Add an aliquot 0,0714 M solution MCpTi sufficient to make the download of the transition metal found in table 3. This mixture is stirred for 30 minutes and then transferred into the reactor for polymerization.

Polymerization

In the autoclave with a capacity of 10 l load 6 liters of anhydrous hexane, comonomer, if required, submit, if required, hydrogen gas, and the contents heated to 80oC, unless otherwise noted. To increase the pressure to the desired level of added ethylene. From the boot of the cylinder under the pressure of the added amount of catalyst on the carrier specified in table 3. Ethylene is continuously fed into the reactor as needed. After the desired polymerization of the line feed of ethylene block, and the contents of the reactor is poured into the sample container. Decanted hexane of the polymer, and the polymer is left overnight to dry, and then weighed to determine yield.

In the experience of 22 temperature is 70oC, the reactor was added 100 ml of co monomer 1-octene to obtain an ethylene/1-actinophage sopulimaen to obtain an ethylene/1-actinophage copolymer with a density of 0,9230 g/cm3.

Private polymerization conditions and results are summarized in table 3. The data in this table show that polymers with a high bulk density can be obtained from the catalyst components on the carrier, obtained using different combinations of heat treatment and/or leaching. The greatest efficiency showed components of catalysts on the media and catalysts containing more than 20 wt.% Al. Excellent efficiency is obtained with the components of the catalysts on the media, subjected to dispersion in toluene at 90oC. Poor bulk density (experiments 1 to 3) obtained with the components of the catalyst on the carrier, which had not been subjected to any heat treatment at a sufficiently high temperature or for a long enough time, nor enough well washed.

Example 20

The method of example 2 is repeated, using 6.2 g of silica SD 3216.30 and 68 g of a solution of MAO to obtain 22.1 g of free flowing powder with aluminium content of 27.8%. In 75 ml of toluene suspended 11 g of the media and add 440 µmol MCpTi book (6.16 ml 0,0714 M solution in hexane). The mixture is stirred for 1 hour, and then at reduced pressure to remove the solvent, and the residue is heated at th phase is washed with 2 portions of 50 ml of fresh toluene, and then dried in vacuum at 100oC for 1 hour. Mass is equal to 9 g, the aluminum content of 24.8%, the content of Ti 40 μmol/g

Example 21

The method of example 6 is repeated, using 12.1 g of silica SD 3216.30 and 327 g of a solution of MAO with obtaining free flowing powder. In vacuum at 150oC for 2 hours, heated to 9.1 g of this powder and receive material aluminum content of 30.7%. In 35 ml of toluene suspended 3.5 g of this powder and add 140 µmol MCpTi (1,96 ml 0,0714 M solution in hexane), and the mixture is stirred for 1 hour. The mixture is filtered, and the carrier was washed with 6 portions of 50 ml of fresh toluene until the discoloration of the leaching solvent, and then dried in vacuum at 20oC for 1 hour. Mass is equal to 22.0 g, the content of Ti 30 µmol/g

Example 22

The method of example 2 is repeated using 3.0 g of silica SD 3216.30 and 82 g of a solution of MAO with the receipt of 10.5 g of free flowing powder. In 50 ml of toluene suspended 4,85 g of this powder, and the mixture is stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 20 ml of fresh toluene and then 2 hours and heated in vacuum at 150oC. Mass equal to 2.1 g, the aluminum content of 14.9%. Add MCpTi according to the method of example 19.

Example 23

Into the flask VM is 82 ml 0.0714 M solution in hexane), and the mixture is stirred for 2 hours. Add 101 g of a solution of MAO, and the mixture is stirred for 16 hours. After that, the solvent is removed under reduced pressure at 20oC obtaining free flowing powder.

Following the General polymerization method of example 19 by using special conditions indicated in table 4, were obtained the results given in the same table.

The data in this table show that if metallocen added before heat treatment at 150oC (example 20), then we obtain catalysts with low activity. Reasonable bulk density is achieved, if metallocen add stage after heating but before stage washing (example 21). Good bulk density is obtained if stage leaching perform at the stage of heating (example 22). Inactive catalyst is obtained if metallocen added to the silica gel first (example 23).

Example 24

Repeating the method of example 1, except that after removal of the solvent from the mixture MAO/silica under reduced pressure at 20oC, portion of the obtained powder is subjected to a two-hour heat treatments and optional leaching, as indicated in table 5. After these treatments compa extractable aluminum, on the other hand, is used in the polymerization. All stages of leaching and extraction is carried out for 1 g of the carrier 10 ml of toluene, stirred for 1 hour, then filtered and washed with 2 portions of 5 ml of toluene, 1 g of the initial carrier. According to the General method described in example 19, receive catalysts on the media. All polymerization performed with a total pressure of 15 bar and 80oC for 1 hour. The results are given in table 6. The examples show that if the percentage of extractable aluminum is lower than 10, it achieved excellent bulk density.

The only heat treatment at 175oC in experiment 1 without any washing allows to obtain polymers with high bulk density.

Example 25

The method of example 2 is repeated using 5 g of silica and 101 g of a solution of MAO with obtaining free flowing powder. This powder is heated in vacuum at 100oC for 8 hours to obtain 12.5 g of a substance. The carrier is suspended in 125 ml of toluene at 90oC, and the mixture is stirred for 1 hour. The mixture is filtered, and the carrier was washed with 2 portions of 50 ml of fresh toluene (90oC) and then dried in vacuum at 100oC for 1 hour. Mass is equal to 11.1 g, a specific content of aluminium is 26 the tion is carried out at a total pressure of 15 bar, 80oC for 1 hour. The results are summarized in table 7.

Example 26

To obtain a catalyst component on the carrier essentially repeat the following the method of example 5 of U.S. Pat. USA 5240894. To 35 ml of toluene is added 0,58 µmol MCpTi (8.1 ml 0,0714 M solution). To the resulting add 75 ml of 10 wt.%-aqueous solution of MAO in toluene, and the mixture is stirred for 15 minutes. Add 5 g of silica (SD 3216.30 pre-aged at 250oC for 3 hours), and the mixture is stirred for 20 minutes. The mixture is heated at 65oC in a vacuum of 75 minutes, and the dried solid phase is washed h ml of pentane, filtered and dried in high vacuum; get 8 g of yellow solid aluminum content of 18.1 wt.%. Extraction with toluene at 90oC, followed by drying to give a yellow solid aluminum content of 16.2 wt.%. The percentage of extractable aluminum is 10.5%. When washing, as well as by extraction with hot toluene, part MCpTi is lost, as indicated by the yellow color has stood the top layer. Using the catalyst on the carrier, not treated with hot toluene (experiment 1), and using the catalyst treated with hot toluene (experiment 2), following the General method of example 19 were carried out Optim catalyst (from 10.5% of extractable aluminum) gives poor bulk density. Extraction of the obtained catalyst hot toluene greatly increases the bulk density (experiment 2).

Example 27

In a flask with a capacity of 1000 ml with continuous stirring load 508 g of a 10% solution of MAO in toluene and 25 g of SYLOPOL 2212 with a moisture content of 3.5%. The mixture is then stirred for further 2 hours and then at 20oC under reduced pressure to remove the solvent to obtain a free flowing powder. This powder is then heated in vacuum for 2 hours at 175oC. This powder is re-suspended in 700 ml of toluene, and the mixture is boiled for 1 hour under reflux. The mixture is filtered, and the carrier was washed with 2 portions of 200 ml of fresh toluene at 100oC. Then, the carrier is dried in vacuum at 120oC for 1 hour. Receive and 63.9 g of the carrier with aluminium content of 26.4%. Sample media suspender in toluene, stirred for 1 hour, and then carry out the measurement of particle distribution on the device Malvern Mastersizer X. Measurement shows that d(v, 0.5) is approximately equal to 12 microns. According to this method, then get the other components of the catalyst on the carrier, having a slightly different load aluminum.

Weighted number of carrier components suspended in hexane, and the mixture premesis is methyl)silane} -4-1,3-pentadentate (hereinafter MCpTi in experiment 4). Consistently add MCpTi or MCpTi(II) (in ISOPARTME) in amounts shown in table 9. Thus obtained catalyst on the carrier used in the suspension polymerization at 80oC, as in the General form described in example 19. Other conditions and results are shown in table 9. These results show that a long period of dispersion before addition of the compound of the transition metal leads to an increase in catalytic activity (compare with table 3).

Example 28

In the autoclave with a capacity of 3 l load specified in table 10 the number of 1-octene, and then add ISOPARTME in a quantity sufficient to achieve a total volume of 1500 ml Injected with 300 ml of hydrogen gas, and the reactor is heated to the desired temperature. Add enough ethylene to bring the system pressure up to 30 bar. To initiate polymerization of the added catalyst on the carrier and continuously as expenditure is added to the reactor ethylene. After the desired polymerization of the block the line of feed of ethylene and the contents of the reactor is poured into the sample container. The polymer was left overnight for drying, cularly masses (Mw/Mn) is calculated according to the distribution chromatography, and the melt index I2determined in accordance with ASRM D-1238-65T (at 190oC and a load of 2.16 kg).

For polymerization used the following catalysts on the media. Media with aluminium content of 23.8% on degradirovannom silica SD 3216.30 was obtained in a manner similar to Example 10. In experiments 1 through 3 0.075 g of the carrier suspended in ISOPARTMwas stirred for a few minutes. Was added an aliquot 0,0714 M solution MCpTi sufficient to create download titanium 20 µmol/g This mixture was stirred for a few minutes, and then introduced into the reactor for polymerization. In experiments 4 through 6 were used to 0.3 g of the carrier when the same loading titanium.

In the process of solution polymerisation catalysts on the media show good performance and give polymers with a narrow distribution of molecular masses.

Example 29

In the present example describes experiments on continuous polymerization. These tests were carried out using catalysts on a carrier obtained according to a manner analogous to example 27. The medium contained 25 wt.% aluminum. In all experiments, the loading MCpTi was 40 μmol/g

In capacitive reactor mestimation and the catalyst on the carrier, and suspension of the resulting product is continuously removed. The total pressure of all experiments on the polymerization equal to 15 bar. Exhaust suspension is passed into the relief tank to remove solvent, and collecting the dry free flowing powder of the polymer. Table 11 summarizes the conditions and properties of the products obtained. The melt index is determined in accordance with ASRM D-1238-65T (at 190oC and a load of 2.16 kg, reduced: I21). The content of butene in the polymer was determined by infrared spectroscopy. The results show that the powders of polymers with a high bulk density with preservation of the morphology of the particles can be obtained in a wide range of densities.

1. Component of the catalyst on a carrier, including a carrier and alumoxane containing partially extracted by toluene aluminum, characterized in that alumoxane contains 15 to 40 wt.% aluminum from the General mass media and alumoxane, with not more than 10 wt.% aluminum extracted for one hour at 90oC using 10 ml of toluene, 1 g of the catalyst component on the carrier.

2. Component of the catalyst under item 1, characterized in that alumoxane extracted no more than 9 wt.% aluminum.

3. Component of catalyst according to PP.1 Disa fact, that alumoxane is methylalumoxane.

5. Component of catalyst according to PP.1 to 4, characterized in that alumoxane contains 20 to 40 wt.% aluminum from the General mass media and alumoxane.

6. A method of obtaining a catalyst component on the carrier by contacting media alumoxane to ensure fixation of the latter on the media and rinsing media in one or more stages of the aromatic hydrocarbon solvent to remove not zafiksirovalos on the media alumoxane, characterized in that the fixing alumoxane on the media carried out by heating the media containing alumoxane in the form of a free current of powder in an inert atmosphere at a temperature of 75 - 250oC with the education component, containing 15 to 40 wt.% aluminum from the General mass media and alumoxane, in which not more than 10 wt.% aluminum extracted for one hour at 90oC using 10 ml of toluene, 1 g of catalyst component.

7. The method according to p. 6, wherein the flushing medium is carried out in conditions of boiling under reflux, suspending in an aromatic hydrocarbon solvent component of the catalyst on the carrier.

8. The method according to p. 7, characterized different topics the fixing at a temperature of 75 - 250oC is carried out at reduced pressure.

10. The catalyst on the carrier including a component of the catalyst on the carrier including a component catalyst consisting of a carrier and alumoxane and the transition metal compound, characterized in that it contains a component of the catalyst on the carrier according to any one of paragraphs.1 - 5.

11. The catalyst according to p. 11, characterized in that the compound of the transition metal is mononitrobenzene compound of a transition metal of group IV with bridge connection or biscyclopentadienyl compound of a transition metal of group IV with bridge connection.

12. The catalyst p. 10 or 11, characterized in that the molar ratio of atoms of aluminum and the transition metal is 1 to 5000.

13. The catalyst according to any one of paragraphs.10 to 12, characterized in that it contains 0.1 to 1000 micromoles of compounds of the transition metal per 1 g of the carrier.

14. The catalyst according to any one of paragraphs.10 - 13 in formelementname form, characterized in that will polimerizuet olefin in the presence of catalyst on the carrier.

15. A method of obtaining a catalyst on the carrier, including the production of catalyst component according to any one of paragraphs.6 - 10 and obeegadoo metal provided after adding the transition metal compounds thus obtained product is not exposed to a temperature equal to or higher than the temperature of decomposition of the compound of the transition metal.

16. The method according to p. 15, characterized in that the compound of the transition metal is added after the stage of heating.

17. The method according to p. 16, characterized in that the compound of the transition metal is added after the stage of washing.

18. The method according to any of paragraphs.15 to 17, characterized in that the compound of the transition metal is mononitrobenzene or (monosubstituted) cyclopentadienyls compound of a transition metal of group IV with bridge connection or biscyclopentadienyl or (benzamidine) cyclopentadienyls compound of a transition metal of group IV with bridge connection.

19. The method according to any of paragraphs.15 to 18, characterized in that the molar ratio of atoms of aluminum and the transition metal is 1 to 5000.

20. The method according to any of paragraphs.15 to 19, characterized in that the catalyst on the carrier contains 0.1 to 1000 micromoles of compounds of the transition metal per 1 g of the carrier.

21. The method according to any of paragraphs.15 to 20, characterized in that will polimerizuet olefin in the presence of the polyaddition monomers, namely, that one or more monomers for polyaddition in contact with the catalyst on the carrier according to any one of paragraphs.10 to 14 in terms of polyaddition.

23. The way polyaddition on p. 22, held in conditions of suspension or gas-phase polymerization.

 

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