The catalyst for polymerization of olefins, process for its production and method for producing olefin polymer

 

(57) Abstract:

Usage: for the polymerization of olefins. The essence: a catalyst for polymerization of olefins, consisting of microporous media with pore volume equal to at least 50 % of the total volume of the medium, and a pore size from 0.1 to 10 μm, and formed thereon a catalytically active portion, which is the product of interaction iluminacin and metallocene with microporous polymer carrier. Described is a method of obtaining the above-mentioned catalyst and method for producing olefin polymer using the above catalyst. 2 s and 5 C.p. f-crystals.

The invention relates deposited on a substrate (heterogeneous) catalyst used for the polymerization of olefins.

Known methods for producing polyolefins using the catalyst comprising the component of the transition metal type metallocene and component socializaton, oligomeric aluminum compounds of the type iluminacin (in most cases methylaluminoxane), which with high activity give polymers and copolymers with a narrow distribution of molar masses (EP-A-69951)

A serious disadvantage of these soluble (homogeneous) metallocen-methyl is a substance education is a strong plaque on the walls of the reactor and stirrer.

A known catalyst for polymerization of olefins comprising the polymer carrier and formed thereon a catalytically active portion, which is the product of interaction of metallocene (in particular, zirconocene), iluminacin formula II.

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for linear type iluminacin and/or formula III:

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for the cyclic type luminokaya,

where R is - (C1-C6)alkyl, p is greater than 2,

and the polymer carrier. The polymeric carrier is a thermoplastic, namely a polyolefin selected from the range of: polyethylene, polypropylene, or polyester selected from the range of: polyamides, polystyrene, polyvinyl chloride, polymethyl methacrylate, etc. particle Diameter of the used polymer carrier ranges from 5 to 200 μm (patent US 4874734, class C 08 F with 4.64, 1989).

Known catalyst has a number of disadvantages, in particular, in the conditions of polymerization with the use of polymeric carriers occurs the separation of the catalyst components from the carrier under the action of a suspending agent or liquid monomers.

The objective of the invention is to find a catalyst system and method of polymerization, to whom to give a relatively inexpensive catalyst, which can be universally used without reducing the activity of the catalyst.

The problem is solved by the simple method of application, which can be universally used in all types of polymerization when the reaction product of alyuminiiorganicheskikh compound A and the compound of the transition metal B reacts with a special polymer component carrier C.

Thus, the subject invention is a polymerization catalyst, deposited on a substrate, which can be obtained by reacting the reaction product iluminacin and at least one metallocene with microporous polymer carrier.

According to the invention can also be used mixtures of different alumination and/or more metallocenes. By using multiple metallocene especially available polymers with a wide distribution of molar masses and the so-called reactor mixture. However, preference is given to using one metallocene. As iluminacin mainly use the connection formula II

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for the linear type and/or of the formula III

< / BR>
for the cyclic type,

in formulas II and III, the radicals R are identical or youtd, and p denotes an integer from 2 to 50, mostly from 10 to 35.

Mainly the radicals R are identical and are methyl, isobutyl, H.-butyl, phenyl or benzyl, particular preference is given to the stands.

If the radicals R are of different value, they mean primarily methyl and hydrogen, methyl and isobutyl or methyl and H.-butyl, with hydrogen or isobutyl or H.-butyl contain predominantly of 0.01-40% (number of radicals R).

Iluminacin can be obtained in various ways known methods. One of the methods is, for example, that aluminiumindustrie connection and/or hydrodesulphurisation compound reacts with water (gaseous, solid, liquid or bound, for example, water of crystallization) in an inert solvent (such as, for example, toluene). To obtain iluminacin with different altergroup R two different aluminiumrail react with water according to the demanded connection and reactivity (cf. S. Pasynkiewicz, Polyhedron, 9/1990/ 429 and EP-A 302 424).

The exact structure of alumination II and III is unknown.

Regardless of the type of receiving common to all the solutions iluminacin is changing the content of the original joint In the catalyst according to the invention as a compound of a transition metal is used metallocen. You can use basically any metallocen regardless of structure and composition. Metallocene can form a bridge and not to form it, to have the same or different ligands. We are talking about compounds of metals of groups IVb, Vb or VIb of the periodic system, for example, compounds of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably zirconium, hafnium and titanium, a special advantage is the connection of zirconium.

Such metallocene known and described, for example, in the following patent applications: EP-A-336127, EP-A-336128, EP-A-387690, EP-A-387691, EP-A-302424, EP-A-129368, EP-A-320762, EP-A-284707, EP-A-316155, EP-A-351392, US-A-5017714, J. Orgamet. chem., 342 (1988) 21.

Of particular interest are metallocene, specially should call zirconocene that contain derivatives indenyl as ligands. It mainly concerns the following compounds of the formula I

< / BR>
where

M1metals of group IVb, Vb or VIb of the periodic system;

R1R2are the same or have different values and mean a hydrogen atom, a C1-C10-accelgroup, C1-C10-alkoxygroup, C6-C10-allgraph, C6-C10-alloctype, C2-C10-altergroup, C-group, or halogen atom.

The radicals R3the same or have different values and mean a hydrogen atom, a halogen atom, a C1-C10-accelgroup, which can be galogenirovannami, C6-C10-allgraph,- NR2, SR, -OSiR3-SiR3or PR2-the rest,

where

R is a halogen atom, a C1-C10-altergroup or C6-C10-allgraph;

R4-R8have the meanings indicated for R3or adjacent radicals R4- R8form with the atoms connecting them aromatic or aliphatic ring;

R9< / BR>
< / BR>
= BR10, = AIR10, -Ge -,- Sn -, - O- -S-, = SO, = SO2, = NR10, = CO, = PR10or = P(O)R10,

if this

R10and R11the same or have different values and mean a hydrogen atom, a halogen atom, a C1-C10-accelgroup, C1-C10-coralcalcium, C6-C10-allgraph, C6-C10-torridgroup, C1-C10-alkoxygroup, C2-C10-altergroup, C7-C40-arylalkyl, C8-C40-arylalkyl, C7-C40-alkiliruya or R10and R11form a ring with the atoms connecting them, and

M2silicon, germanium or tin.

4, 5, the AK rule,

M1-Zirconia;

R1and R2are equal and denote methyl or chlorine, especially chlorine;

R3-R8denote hydrogen or C1-C4-alkyl,

R9does

< / BR>
thus R10and R11the same or have different values and mean C1-C4-alkyl or C6-C10-aryl. In particular, R10and R11the same or have different values and means methyl or phenyl.

Ligands indenyl and tetrahydroindene in formula I is substituted mainly in 2-, 2,4-, 4,7-, 2,6-, 2,4,6-, 2,4,5,6- and 2,4,5,6,7-position, especially in the 2,4,6-position. Substituents are predominantly C1- C4-altergroup as, for example, methyl, ethyl or isopropyl. 2-polozenie substituted mainly stands.

Of particular importance are further such compounds 1, in which the substituents in the 4 - and 5-position residue indenyl (R5and R6) form together with the atoms connecting them benzolive ring. This condensed ring system may be substituted by radicals from the values of R3- R8. As examples of such compounds should be called dimethylselenide/2-methyl-4,5-benzhydryl/circondato the singing of stereoregularity.

Metallocene 1 and metallocene described in these patent applications, it is possible, for example, be obtained according to the following reaction scheme:

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X = Cl, Br, J, O-tosyl; H2RcH2Rd= ligands, for example, (Thames.) inden;

* additional stage hydrogenation, if, for example, ligands indenyl must be converted to the ligands tetrahydroindene.

The ways of getting mainly known from the literature; cf. Journal of Organometallic chem. (1985)63-67, EP-A-320762 and applications referenced concerning metallocenes.

To obtain compounds 1 as the source materials used indene, substituted in various ways, (H2RcH2Rd; cf. the following reaction scheme). Such derivatives of indene currently known and available commercially. Substituted in a special way indene can be obtained by the means indicated below:

a) H2RcH2Rd=

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The synthesis takes place according to or analogously to the following examples, given in J. Org, Chem., 49(1984) 4226-42374, J. Org Soc, Peskin II, 1981, 403-408, J. Am. Chem. Soc., 106 (1984) 6702, J. Am. Chem. Soc., 65 (1943) 567, J. Med. Chem., 30 (1987) 1303-1308, Chem. Ber. 85 (1952) 78-85.

b) H2RcH2Rd=

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is possible in two different ways:

B1) as starting compound used ketoaldehyde formula specified in the following reaction scheme, whose obtaining is known (Synthesis, 1985, 1058).

The reaction of this ketoaldehyde with cyclopentadiene is carried out in an inert solvent in the presence of a base.

Mainly used alcohols such as methanol, ethanol or tert.-butanol, especially methanol.

As grounds used a lot of connections. As examples of the hydroxide of alkali and alkaline earth metal alcoholate of alkali and alkaline earth metals such as sodium methylate, sodium ethylate, tert.butyl potassium, Andy, for example, Isopropylamine lithium or amines.

Mainly used methylate sodium tert. butyl potassium and potassium hydroxide.

The molar ratio of the starting compounds, including applicable base can vary within wide limits.

Preferably the molar ratio ketoaldehyde: cyclopentadiene: base = 1:1-1,5:2-3, especially 1:1, 1:2,5.

The reaction temperature is mainly from -40 to 100oC, especially 0 - -25oC.

The reaction time ranges usually from 10 minutes to 100 hours, the l in the 2-position can be introduced by transformation one-deputizing in the 4-position of the indene in one-deputizing in the 4-position 2-indanone by the Grignard reaction. Subsequent separation of water leads to the formation of 2,4-substituted indeno.

2,4-substituted indene identified as isomers with double bonds, which can be used directly for the synthesis of the corresponding metallocene complexes.

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B2) Another possible and convenient strategy is carried out according to the following scheme:

Substituted in the 2-position of benzylchloride transformed according to the method known from the literature (J. Org. Chem. , 1958, 23, 1437), in the course of the exchange reaction with an appropriately substituted complex fluids malonic acid disubstituted complex fluids malonic acid. Saponification complex diapir and decarboxylation conventional methods leads to the formation of disubstituted derivative of propionic acid.

Ring closure of 2,4-substituted 1-indanone is carried out after the conversion of carboxylic acid in the carboxylic acid chloride by the known methods (reaction Friedel -).

Recovery ketone known methods and subsequent separation of water leads to the formation of 2,4-disubstituted indeno.

c) H2RwithH2Rd=

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Obtaining compounds H2RwithH2R1and X2denote nucleophilic original group, such as, for example, halogen, a hydroxy-group or tailgroup, especially bromine or chlorine.

Get indanone IV and IV

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Indanone can be deposited depending on the position of the groups in the aromatic ring in the form of two stereoisomers of formula IV and IVa. They can be recovered in pure form or in the form of a mixture by methods known from the literature, using a reducing agent such as NaBH4or LiAlH4into the corresponding indanone and then subjected to dehydration using acids, such as, for example, sulfuric acid, oxalic acid, paratoluenesulfonyl, or by treatment with dehydrating agents such as magnesium sulfate, sodium sulfate, aluminum oxide, silica gel or molecular sieves in indeni formula V and Va (H2Rwith/H2Rd) (Bull. Soc. Chim. Fr. 11/1973 / 3092; were obtained 9/1990/3098).

< / BR>
Suitable catalysts for Friedel-are, for example, AlCl3, AlBr3, FeCl3, SbCl5, SnCl4BF3, TiCl4, ZnCl2H2SO4, polyphosphoric acid, H3PO4or melts AlCl3/NaCl; especially AlCl3.

The initial compounds of formulas II and III are known, Artem solvent. Mostly use methylene chloride or CS2. If the original components of the liquid, the customer can withdraw from the solvent.

The molar ratio of the starting compounds, including the catalyst of the Friedel-can vary within wide limits.

The advantage is the molar ratio of compounds II:III:catalyst = 1:0.5 to 1.5:1-5; especially 1:1:2,5-3.

The reaction temperature ranges mainly from 0 to 130oC, especially from 25 to 80oC.

The reaction time ranges usually between 30 minutes and 100 hours, mostly between 2 and 30 hours

The advantage is a mixture of compounds II and III, and optionally add the catalyst for Friedel -. Reverse the order of addition is also possible.

Indanone formula IV and IVa can be cleaned by distillation, column chromatography or crystallization.

Substituted indene can precipitate in the form of isomers with double bonds (V/Va). They can be cleaned by-products by distillation, column chromatography or crystallization.

Based on indeno formula V and Va, they can be used as a mixture of isomers is obtained metallocenes 1 ways,

d) H2RcH2Rd=

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with R12and R13having a value of R4-R8.

These benzododecinium indeno and their further transformation into metallocene occurs according to the reaction scheme given in the end of the description.

Derivatives of naphthalene of the formula A are commercially available or can be obtained by methods known from the literature (Friedee Crafts and Related Reactions, Wiley, new York, 1964, vol. II, page 659-766, Bull. Soc. Chim. Belges 58 (1949) 87, J. Amer. Chem. Soc. 89 (1967) 2411).

The conversion of compounds of formula C occurs by methods known from the literature, by substitution reactions of esters of malonic acids of formula B in basic conditions such as, for example, in the ethanol solutions mutilate sodium (J. Org.Chem. 23 (1958) 1411, J. Am. Chem. Soc 70 (1948) 3569).

The compounds of formula C Malaysia the hydroxides of alkali metals such as potassium hydroxide or sodium, methods known from the literature, and is the decarboxylation of compounds of formula D obtained by thermolysis of dicarboxylic acids by methods known from the literature (J. Org.Chem. 23 (1958) 1441, J. Am.Chem.Soc. 70 (1948) 3569).

The closure ring substituted by benzoindole formula E occurs by methods known from the literature dealing with the s and subsequent cyclization with a catalyst of the Friedel-crafts in an inert solvent, such as, for example, AlCl3or polyphosphoric acid in methylene chloride or CS2(Organometallies 9 (1990) 3098, Bull. Soc. Chim. Fr. 3 (1967) 988, J.Org. Chem. 49 (1984) 4226).

The transformation of the derivatives of besondere formula G occurs by methods known from the literature, by restoring using sodium borohydride or hydride layalina in an inert solvent, such as for example, diethyl ether or THF, or by alkylation with an alkylating means of the formula F or alkylene lithium into the corresponding alcohols or by dehydration of alcohols in acidic conditions such as, for example, using paratoluenesulfonyl or oxalic acid, or by reaction with a dehydrating substances, such as magnesium sulfate or molecular sieves (Organometallies 9(1990) 3098, Alta. Chem. scand. B 30 (1976) 527, J. Amere. Chem. Soc. 65 (1943) 567).

Derivatives of besondere formula G can be also synthesized other, not specified here by synthesis from substituted naftalina in the four stages of synthesis (Bull. Soc.Chim Fr. 3 (1967) 988).

The receiving system ligands of the formula J and become chiral, forming a bridge metallocene formula K, as well as the selection of the desired rectory in principle known (AU-A - 31 478/89, J. were obtained.Chem. 342 (1988) 21, EP 0 284 707, EP 0 320 762).

A downcast metallocene formula 1 can occur by methods known from the literature, for example, by exchange reaction with alkylating means, such as for example, methyl lithium (Organometallils 9 (1990) 1539, J. Amer. Chem Soc. 95 (1973) 6263, EP 0 277 004).

As examples to be used according to the invention metallocenes include the following compounds:

biscyclopentadienyl,

zirconiabased,

biscyclopentadienyl,

bis(methylcyclopentadienyl)zirconiated,

bis(1,2-dimethylcyclopentane)zirconiated,

bis(1,3-dimethylcyclopentane)zirconiated,

bis)1,2,4-trimethylcyclopentanone)zirconiated,

bis(1,2,3-trimethylcyclopentanone)zirconiated,

bis(pentamethylcyclopentadienyl)zirconiated,

beendelivered, bis(tetrahydroindene)zirconiated,

dimethylsilane-bis-1-tetrahydroxyphenylchlorin,

dimethylsilane-bis-1-(2-methyl-tetrahydroindene)zirconiated,

dimethylsilane-bis-1-(2,3,5-trimethyl-cyclopentadienyl)- zirconiabased,

dimethylsilane-bis-1-(2,4-dimethyl-cyclopentadienyl) zirconiated,

dimethylsilane-bis-1-indenyltitanium,

dimethylsilane-bis-1-indenyltitanium,

dimethylheptyl-bis-1-indenyltitanium,

dimethylsilane-bis-1-(2-methyl-indenyl)-zirconiabased,

dimethylsilane-bis-1-(2-methyl-4-isopropylidene)zirconiated,

phenylmethylene-bis-1-(2-methyl-indenyl)-zirconiabased,

dimethylsilane-bis-1-(2-methyl-indenyl)-zirconiabased,

ethyl-bis-1-(4,7-dimethyl-indenyl)zirconiabased,

divinycell-bis-1-indenyltitanium,

dimethylsilane[1-(2-methyl-4-tertbutylphenyl)]-zirconiabased,

methylpenicillin[1-(2-methyl-4-isopropylidene)] zirconiabased,

dimethylsilane[1-(2-ethyl-4-methylindenyl)]-zirconiabased,

dimethylsilane[1-(2,4-dimethylindole)]-zirconiabased,

dimethylsilane[1-(2-methyl-4-ethylidene)]-zirconiabased,

dimethylsilane(2-methyl-4,6-diisopropylphenyl)- zirconiabased,

dimethylsilane(2,4,6-trimethylindium)-zirconiabased,

methylpenicillin(2-methyl-4,6-diisopropylphenol) zirconiated,

1,2-atanderson(2-methyl-4,6-diisopropylphenol)zirconiated,

dimethylsilane(2-methyl-4,5-benzhydryl)zirconiated,

dimethylallyl-(9-feranil)-(cyclopentadienyl)-zirconiabased,

divinycell-(9-feranil)-(cyclopentadienyl)-zirconiabased,

diphenylmethyl-(9-feranil)-(cyclopentadienyl-zirconium-dichloride,

isopropylidene-(9-feranil)-cyclopentadienyl-zirconiabased,

phenylethylamine-(9-feranil)-cyclopentadienyl-zirconiabased,

isopropylidene-(9-feranil)-[1-(3-isopropyl)cyclopentadienyl] - zirconiabased,

isopropylidene-(9-feranil)-[1-(3-methyl)dichloride,

methylphenylamine-(9-feranil)-[1-(3-methyl)cyclopentadienyl] - zirconiabased,

dimethylallyl-(9-feranil)-[1-(3-methyl)cyclopentadienyl] - zirconiabased,

divinycell-(9-feranil)-[1-(3-methyl)cyclopentadienyl] - zirconiabased,

diphenylmethylene-(9-feranil)-[1-(3-tert. -butyl)cyclopentadienyl]- zirconiabased,

and

isopropylidene-(9-feranil)-[1-(3-tert.butyl)cyclopentadienyl]- zirconiabased.

Chiral metallocene use upon receipt of the catalyst according to the invention primarily as a racemate. But you can also use and clean R-form or S-form. Using these pure stereoisomeric forms can be obtained optically active polymer. However, it is necessary to separate mesoform metallocenes, since the polymerization-active center (the metal atom) in these compounds due to mirror symmetry at the Central metal is no longer chiral and therefore it is impossible to get vysokotehnicheskoe polymer. If mesoform not be separated, along with isotactic and syndiotactic polymers obtained also atactic polymer. For certain applications, for example, a soft molded product, or to obtain certain types of polyethylene, this can be the/P> Used according to the invention the microporous polymeric carrier may vary depending on applications, and it may correspond to, for example, the desired product of polymerization. It mainly concerns thermoplastics, such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), Acrylonitrile-butadiene-styrene copolymer (ABS), polyamide (PA, PA-6, PA-12), polymethylmethacrylate (PMMA), or polycarbonate (PC), copolymers, reticulated polymers or polymer mixtures.

The hallmark of polymer carriers C according to the invention is not their chemical composition and their microporous structure. The presence of a microporous structure determines the proportion of the hollow space (pore volume) of at least 50 vol.%, mostly at least 70 vol.%, relative to the total volume of the particles of the carrier material of the substrate (catalyst), a molded product of the media (see below). Total media refers to its external volume excluding volume of pores.

The form of micropores is wrong, often spherical. Micropores are partially connected with each other by small holes then. The diameter of pores is from about 0.1 to 10 microns. The diameter of the holes of the particles of microporous media depends on the subsequent processing and may be irregular or spherical. The particle size of the carrier can, for example, be obtained by any cryogenic grinding and sieving. However, it is also possible to apply the microporous polymer directly as a granulate, plate or membrane to obtain a catalyst system according to the invention, and in this form to apply in a suitable polymerization method.

Obtaining microporous media can occur in different ways.

Thus, polymer (e.g., polypropylene) can be mixed with a second substance (for example, 50 wt.% N, N-bis-/2-hydroxyethyl/-hexadecylamine), which when heated above the melting temperature of the polymer form a single phase mixture, cured by cooling to the formation of the solid matrix.

Then the second component can be removed with a solvent, and remains polymer structure with a spherical micropores in the form of cavities which are interconnected by holes then.

Each time to obtain such microporous materials (substrate) of a substance corresponding to the type of polymer, called also acetoarsenite, as, for example, a mixture of soybean and castor oils, added to the polymer in the extruder and other prednaznachennogo, fibers or membranes are known (cf. for example DE-2737745, EP-B-108601, DE-2833568, EP-A-357021, DE-3327638).

Along with these opportunities there are also other, for example, sintering of fine polymer powders or special methods described in EP-A-289238. Obtaining a microporous polymer carrier, however, is not limited ways described here.

Samples of suitable microporous polymeric carriers are commercially available (for example,RAccurel types of AKZO, such as RAccurel-p,RAccurel PP,RAccurel-PA-6 orRAccurel-PA-12 percent voids (about 75%).

The pore size ofRAccurel materials is 0.5-5 μm (PP), 1.0 to 5 μm (LDPE), 0.5 to 3 μm (PA-6 and PA-12).

The subject of the invention is a method of producing the catalyst according to the invention, deposited on a substrate, for polymerization, characterized in that conduct the reaction product of interaction iluminacin and at least one metallocene with microporous polymer carrier.

Preferably microporous polymeric carrier before it is dried, for example, by processing solutions alkylamine, then washed and rinsed with an inert gas.

This is preimun, heptane, toluene or dichloromethane, enter into interaction with at least one metallocene by intensive mixing, for example, stirring. The reaction temperature is mainly from -20 to +120oC, especially 15-40oC.

The molar ratio of aluminum to transition metal M metallocene within predominantly between 10:1 and 10000:1, especially between 100:1 and 2000:1. The reaction time is from 5 to 120 min, mostly 10-30 minutes

Work mostly with the aluminum concentration is more than 0.01 mol/l, particularly more than 0.5 mol/L. the Reaction is carried out in inert conditions.

Instead iluminacin you can also use a mixture of iluminacin connection alkylamine, for example, trimethyl-, triethyl - or triisobutyl-described aluminum for reaction with metallocenes.

After completion of the reaction the solvent can, for example, partially removed in vacuum conditions or after concentration to be replaced by another solvent. Thus obtained solution shall be appropriately reacting with the porous polymer carrier. When this media is added at least in an amount such that the total pore volume absorbed solution prior to the about 15-40oC, by intensive mixing, for example, by stirring or ultrasonic treatment. Must happen a satisfactory homogenization. Thus, displacement of the inert gas in the pore volume can be accelerated, for example, using short-term pumping.

In principle, the receipt of the catalyst, deposited on a substrate, can also occur during the reaction in a single vessel, i.e., all three original component simultaneously react in a suitable solvent/suspendisse agent. The number of polymer carrier mainly should be such that it was fully absorbed in the total amount of liquid.

The catalyst according to the invention can be in the form of a suspension in an inert suspendium agent, such as, for example, heptane, H.-decane, hexane, diesel oil, or in dry form to enter, if possible, after removal of residual solvent by drying, for example, under vacuum, into the polymerization system.

The catalyst according to the invention can be terpolymerization preferably in the gas phase, in the liquid monomer or in suspension, it is possible to abandon the additive another alyuminiiorganicheskikh connection.

a-CH=CH=Rbwhile Raand Rbthe same or have a different meaning and signify a hydrogen atom or a hydrocarbon residue with 1 to 14 C-atoms, or Raand Rbmay form a ring with the atoms connecting them at a temperature of from -60 to 200oC, a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase in the presence of a catalyst, wherein the catalyst is used the reaction product according to the invention.

The polymerization or copolymerization is conducted in a known manner in solution, in suspension or in the gas phase, continuously or intermittently at one or more stages at a temperature of from -60 to 200oC, mainly from 30 to 80oC, special priority is given to temperatures of from 50 to 80oC. Polimerizuet or copolymerize olefins of the formula Ra-CH=CH-Rb. In this formula, Raand Rbthe same or have a different meaning and signify a hydrogen atom or an alkyl residue with 1 to 14 C-atoms. However, Raand Rbcan also form a ring with connecting C-atoms. Examples of olefins of the formula Ra-CH=CH-Rbare ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-penten, 1-octene, norbornene, norbornadiene, 1,4,5,8-dimethylene.

As molecular weight regulator and/or increasing the activity add, if necessary, hydrogen. The total pressure in the polymerization system is from 0.5 to 100 bar. Mainly the polymerization is carried out at a pressure from 5 to 64 bar.

The catalyst according to the invention is used primarily in concentration in the calculation of the transition metal from 10-3up to 10-8mainly 10-4-10-7mol of transition metal per 1 DM3solvent and 1 DM3volume of the reactor.

If the polymerization is carried out in suspension or solution, then apply an inert solvent, the usual method, which is performed under low pressure Ziegler catalyst. The process is carried out, for example, aliphatic or cycloaliphatic hydrocarbon: as aliphatic and cycloaliphatic hydrocarbons should be called, for example, butane, pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane. You can use the gasoline fraction and gidrirovannoe fraction of diesel oil. Also used toluene. The polymerization is carried out mainly in the liquid monomer.

If used inert solvents, optionally add gazoobraznye the invention the catalyst system, shows only a slight time-dependent decrease in the polymerization activity.

Before adding the catalyst in the reactor can be added to the polymerization system another connection alkylamine, such as, for example, trimethyl-, triethyl-, triisobutyl or izoprenil aluminum in order to make the processing of the inert gas system of polymerization (for example, removal contained in the olefin poisons for the catalyst) at a concentration of from 1:0.001 mmol Al per 1 kg of the contents of the reactor.

The use of additional substances for the catalysis of the polymerization reaction is not, however, in principle necessary, since the catalyst according to the invention is given this advantage can be used as the only catalyst.

On the molar mass of the formed polymer can be influenced by changing the polymerization temperature, and due to periodic changes or multi-step process or multiple metallocene polymer with a wide distribution of molar mass is also available.

In addition, obtained using the solid catalyst according to the invention the molar mass can be determined with the help of the ptx2">

Describes the catalyst does not need to activate in any additional socializaton and completely prevents the formation of plaque on the walls of the reactor.

A significant advantage of the catalyst according to the invention is a simple method of preparation of the catalyst, which is simple and can be repeated and carried out on a larger scale.

Another advantage is that the formed polymer product cannot contaminate inorganic foreign particles, which reduce the mechanical stability of the metal. If polymeric carrier add more, you can get polymer mixtures, which have the additional positive properties (quality).

The following examples should be more detail to illustrate the invention:

All glass devices is maintained at a high temperature under vacuum and washed with argon. All operations are performed in the absence of moisture and oxygen in special vessels.

Solvents person to distil under argon, if it was necessary, fresh over Na/K alloy and kept in special containers.

Mate is by extraction with toluene in a vessel of socket in inert conditions, dried under vacuum and kept in argon.

Microporous HDPE) was obtained as a granular and initially crushed in the mill of the company Retsch after cooling with liquid nitrogen. Used the screen mesh fraction from 100 to 400 microns.

MicroporousRAccurel - powders PP and polyamide-6 was used as sieving fractions up to 200 microns and polyamide-12 as a sieve fraction of 200-400 μm. The volume of voids is for allRAccurel materials 75 vol.%. The pore size is 0.5-5 μm (PP), 1.0 to 5 μm (LDPE), 0.5 to 3 μm (PA-6 and PA-12), engineers 21,6 (190oC) LDPE 4,5, ITR 5 (230oC) PP-21. (ITR - melt flow index). Above the melting point of the polymers were measured by the DSC method for the second melting (10oC/min).

Determination of aluminium iluminacin happens after hydrolytic melt in water and sulfuric acid by complex metric titration on Shwarzenbach.

Methylaluminoxane obtained as a 10% toluene solution from the company Schering AG and contains by definition aluminum 36 mg Al/ml Average degree of oligomerization according to the lowering of the freezing point in benzene is p = 20.

Example 1. A solution of 1 mmol of biscyclopentadienyl in 1 ml of toluene is mixed with 10 ml of 10 ve is L. In parallel, 4 gRAccurel-PA-6-powder sieve fractions below 200 microns dried under vacuum and flushed with argon. The powder carrier is added to the solution of the catalyst until then, until you reach a homogeneous distribution.

The polymerization. The dried reactor-mixer with a capacity of 1.5 DM3washed to remove oxygen, nitrogen and filled with 0.9 DM3inert diesel oil (boiling point 100 to 200oC). After washing with ethylene get a temperature 70oC and the catalyst is optionally added as a powder. Then no additional activator at a pressure of 7 bar carry out the polymerization of ethylene. After 1 h the pressure decrease in the reactor, the polymer is filtered from the suspension and then dried for 12 h in a vacuum drying Cabinet. Obtain 18 g of polyethylene powder with a bulk weight 0,253 kg/DM3and the coefficient of viscosity 389 cm3/, Polydispersity by GPC is Mw/Mn = 2,6. In the reactor does not form any deposits on the walls or the agitator.

Example 2. Repeat example 1, the difference is that 4 gRAccurel-PA-12 powder sieve fractions from 200 to 400 μm is used as the carrier. After polymerization policedepartment (GCP) is Mw/Mn = 2,5. Does not form any deposits on the walls of the reactor and stirrer.

Example 3. Repeat example 1, the difference is that as media use 4 gRAccurel-HDPE-12 powder. After polymerization obtain 14 g of polyethylene powder with a bulk weight of 0.137 kg/DM3and coefficient of viscosity of 390 cm3/,

The polydispersity (GPC) is Mw/Mn = 2,7. If this does not form any deposits on the walls of the reactor and stirrer.

Example 4. 65 gRAccurel PP powder sieve fraction < 200 μm, dried at 210-4mbar and washed with argon. In parallel to 11.7 mg biscyclopentadienyl dissolved in 300 ml of 10 wt.% solution methylaluminoxane in toluene and stirred for 15 minutes the Solution is then concentrate under vacuum to a volume of 40 ml and add the dried powder. After short-term use of vacuum gas contained in the pores of the carrier, removed, and the solution is completely absorbed. After another 10 min of intense mixing receive homogeneous, consisting of a fine particle powder with good flowability. Processed using an inert gas reactor with a capacity of 180 DM3fill 80 l of diesel oil (boiling point 100 to 200oC) heat up through the locks. Simultaneously, the pressure of ethylene is increased up to 7 bar, and the temperature is kept constant by cooling to 70oC. After 2 h of polymerization in the reactor is a decrease in pressure, and the suspension is filtered through Nooch filter. After drying in an oven under vacuum conditions get of 5.4 kg of polyethylene in accordance with the falling out time of contact 9.6 (kg/(mmol h bar)) and with a bulk weight of 164 g/DM3. The product has a density 0,9438 g/cm3when the coefficient of viscosity at 454 cm3/g and polydispersity (GCP) Mw/Mn = 2,7. There are no deposits on the walls of the reactor and stirrer.

Example 5. In a special flask under argon 5.1 mg rat-dimethylsilane-bis-1-2/-methylindenyl/zirconiabased dissolved in 40 cm3toluene solution of methylaluminoxane, within 15 min of settling interact with methylaluminoxane.

The resulting solution was concentrated under vacuum to 8 ml.

To this solution is added under argon 8 g of driedRAccurel PP powder (< 200 μm), and by stirring the sample evenly distribute the powder; in the end to produce a powder with good flowability.

In parallel, the dried reactor with a capacity of 16 DM3wash out nitrogen is e powder load through a system of holes in the reactor, system polymerization using heat heated to the polymerization temperature of 70oC (10oC/min), and this temperature is maintained for 1 hour by cooling. The polymerization is then stopped (add 5 ml of isopropanol), in the reactor lower pressure, and open it. After drying the product under vacuum conditions receive 0.4 kg of polypropylene with a coefficient of viscosity of 145 cm3/,

The average particle diameter d50is according sitonomy analysis of 650 μm with a portion of the fine grain fraction (< 100 μm) in 1 wt.%. There are no deposits on the walls of the reactor and stirrer.

The example for comparison. To obtain catalyst 5.2 mg rat-dimethylsilane-bis-1-(2-methylindenyl)zirconiated dissolved in 20 cm3toluene solution methylaluminoxane and conduct the reaction with methylaluminoxane at 15-min exposure. In parallel, the dried reactor with a capacity of 16 DM3washed with nitrogen and filled 10 DM3liquid propylene. In this reactor type 30 cm3toluene solution methylaluminoxane and stirred at 30oC for 15 minutes

Then the catalyst was ready this time, served in the reactor and conducting the polymerization as in example 5.

The average particle diameter d50according sitonomy analysis is 350 μm.

Example 6. In a special flask dissolve under argon to 5.5 mg of isopropylidene(9-feranil)(cyclopentadienyl)-zirconiabased 4 cm3toluene solution methylaluminoxane and at 15-min exposure carry out the reaction with methyl aluminum.

The resulting solution was concentrated under vacuum to 10 ml of this solution was added under Ar 10 gRAccurel-PA-6 powder sieve fraction small 200 μm and care when shaken samples of a uniform distribution in the powder.

Get a powder with good flowability.

In parallel, the dried reactor with a capacity of 16 DM3washed with ethylene and filled 6 DM385%-aqueous solution of norbornene in toluene. If 70oC in the reactor is set to the partial pressure of ethylene of 6 bar, and powdered catalyst loaded into the reactor through a system of locks. During the subsequent one-hour polymerization, the partial pressure of ethylene by additional dosing is constantly maintained at the level of 6 bar.

Then in the reactor gas pumped, mixed with 100 cm3water in those whom she stirred for 15 min and the polymer precipitated in the sludge is filtered off, well washed with acetone.

After drying under vacuum at 80oC get 375 g of ethylene-norbornene copolymer, which has a coefficient of viscosity at 219 cm3and the glass transition temperature of 152oC.

1. The catalyst for polymerization of olefins, comprising a thermoplastic polymer carrier and formed thereon a catalytically active portion, which is the product of interaction iluminacin and metallocene with thermoplastic polymer carrier, characterized in that thermoplastic polymer carrier used microporous polymeric media with a pore volume of at least 50% of the total volume of media and pore size of 0.1 to 10.0 μm.

2. The catalyst p. 1, characterized in that thermoplastic polymer carrier used polyethylene, polypropylene, polystyrene, polyvinyl chloride, Acrylonitrile - the best choice copolymer, polyamide, polymethylmethacrylate or polycarbonate.

3. The catalyst PP.1 and 2, characterized in that as iluminacin used as a compound of General formula II

< / BR>
for the linear type and/or General formula III- C18-allgraph, benzyl or hydrogen;

p = 2 to 50.

4. The catalyst according to one or more paragraphs. 1 to 3, characterized in that as metallocene use zirconocene.

5. The method of producing catalyst for polymerization of olefins p. 1 by reaction of the product of the interaction iluminacin and metallocene with thermoplastic polymer carrier, characterized in that thermoplastic polymer carrier used microporous polymeric media with a pore volume of at least 50% of the total volume of media and pore size of 0.1 to 10.0 μm.

6. The method of obtaining the olefin polymer by polymerization or copolymerization of an olefin of the formula

Ra-CH = CH-Rb,

where Raand Rbthe same or different, is hydrogen or a hydrocarbon residue with 1 to 14 carbon atoms, or Raand Rbmay form a ring with the atoms connecting them,

at a temperature of from -60 to 200oC and a pressure of 0.5 to 100.0 bar, in solution, in suspension or in the gas phase in the presence of a catalyst, wherein the catalyst used catalyst under item 1.

7. The method according to p. 6, wherein conducting the polymerization or copoly the

 

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