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

 

(57) Abstract:

The invention relates to a catalyst for polymerization of olefins on the media containing the product of the interaction metallocene component (b) and alyuminiiorganicheskikh connection to media (A) obtained by reacting at least one alyuminiiorganicheskikh connection with dry media under inert conditions with subsequent hydrolysis of the resulting suspension by adding water. Also described is a method of obtaining catalyst and method for producing polyolefin using a specified catalyst. The resulting catalyst has a high activity, completely prevents the formation of deposits in the reactor. The method is simple and easy to use. 3 S. and 8 C.p. f-crystals.

The invention relates to a deposited catalyst /heterogeneous/, which can be used in the polymerization of olefins.

Known methods for producing polyolefins using homogeneous catalytic systems containing the component of the transition metal type metallocene and component socializaton, the oligomeric compound of aluminum type alumoxane, usually methylalumoxane "MAO", which has a high AK is ESD a disadvantage of these soluble catalytic systems metallocen/methylalumoxane in ways where the polymer is formed in the form of a solid product, is the formation of thick deposits on the walls of the reactor and the stirrer. These deposits are formed by agglomeration (Polymer Commun. 32. (1991) 58) polymer particles, and if metallocen or alumoxane or both are used in the form of a solution in a suspension medium. Sediments of this type of equipment should be regularly removed as they quickly reach a considerable thickness, high strength and prevent heat exchange with a cooling medium.

Attempts were made to create the catalyst on the carrier, mixing MAO and metallocene with inorganic carriers (EP 206794). To improve the medium has been proposed (WO 88/01626) special material processing device of adhesion promoters. In addition, it is known (EP 295312) that the solubility used methylalumoxane can be lowered in a complex way due to the non-polar solvents such as n-decane. However, these helper methods are not efficient enough and lead, for example, to the separation of aluminum or components of the transition metal in a typical environment, suspension polymerization or polymerization in solution.

Alternatively, it was suggested to get mnoi suspension as a carrier for metallocene (EP 323716) or transfer the entire reaction medium of trimethylaluminum, water-containing SiO2and metallocene, in the polymerization reactor and then conduct polymerization (EP 170059). However, all these methods initially result in getting methylalumoxane dissolved in the reaction medium, which eliminates the advantages of the medium, and, secondly, alumosilicate media have significantly lower polymerization activity, as it only defines the full stoichiometry, and the local control of the stoichiometry of the reaction of water and trimethylaluminum inadequate.

Therefore, the aim was to find a generally applicable method of fixation metallocene polymerization catalysts on a carrier, which would be simple and inexpensive to implement, and which can be universally used without a substantial reduction in catalyst activity.

Convenient and simple method of applying to the media, which is universal in application in all polymerization processes, there is in the case, if alyuminiiorganicheskikh component A of the catalyst on the carrier interacts with the soluble ORGANOMETALLIC component of the catalyst B. the Use alyuminiiorganicheskikh A component on the carrier prevents any removal of any aluminum compounds or transition metal is Skye, the system does not require any additional socialization to activate and completely prevents the formation of deposits in the reactor.

An additional advantage of the catalytic system according to the method of the present invention is that it is possible to dispense with aromatic solvents, and accordingly the resulting sample will not be trace impurities aromatic hydrocarbons. Such products have the advantage when used in medicine and food industry.

To obtain alyuminiiorganicheskikh connection on the media component of A catalyst, the carrier is suspended in a solution of at least one compound alkylamine in inert conditions, and this suspension hydrolyzing by adding water.

To obtain alumoorganic connection on the media /the catalytic component A/ media suspended in a solution of at least one compound alkylamine in inert conditions, and this suspension hydrolyzing water.

As media use oxides of silicon or aluminum, which can optionally contain one or more of the oxides of Al, K, Mg, Na, Si, Ti or Zr, the surfaces of which can be further processed to impart hydrophobicity due to the reaction with alkylsilane, alkylalkoxysilane, alkoxysilane, silazane or other alkyl uume, thermostat in the heated fluidized bed or in other ways. Processed beforehand so the carrier has a residual water content, which can be removed by annealing at 1000oC for 2 hours, to content less than 3 wt.%.

Inorganic media that can be used are oxides obtained flaming pyrolysis combustion elemental halides, such as CHLOROSILANES H2SiCl4-hin a hydrogen-oxygen flame, or those that can be obtained in the form of silica with a specific distribution of particle sizes and shapes.

To obtain a catalytic component A described medium is metered into a solution of at least one compound alkylamine formula AIRR1R2where the radicals R, R1and R2may be the same or different and are a group of C1-C6of alkyl, C1-C6-foralkyl, group C6-C18- aryl, - C6-C18Vtoraya or hydrogen, preferably the stands, ethyl, isopropyl, isobutyl or n-bootrom, in inert conditions, and suspended by stirring, pumping, or any other means. Native isolates choose so to be suspended a maximum of 20 wt.%, preferably up to 10 wt.% media. In addition to the known aromatic solvents such as toluene, can also be used such as aliphatic solvents, such as pentane, hexane, heptane, n-decane or diesel oil boiling range 60-300oC/.

To the thus prepared suspension media carefully add water or solutions, mixtures or emulsions of water with other solvents at temperatures from about -20 to +60oC, cooling and thorough mixing, either in the system with forced circulation with significant turbulence, or in some other way. Water can be fed continuously or in small portions, and the full amount of water is between 50 mol.% and 100 mol. %, preferably between 50 mol.% and 80 mol.% in the calculation of the number of moles of aluminum in the source alkylamino connection.

The catalytic component A, obtained in this way can be washed and prepared in the form of a suspension, or re-decant, or select by filtration, washed, and then suspended again or dried.

However, the catalytic component A can be obtained similarly to other methods of obtaining MA the carrier in a solution of the compound alkylamine. Methods of this type are described, for example, in DE 3731665 and DE 4004477.

The catalytic component B is metallocenes, or a mixture of more than one metallocene.

The catalysts obtained by the use of more than one metallocene most applicable to obtain the so-called reactor blends with bi - or multi-modal molecular weight distributions.

In principle can be used any metallocene, regardless of structure and composition. Metallocene can be with bridges or without them, and can contain identical or different ligands. Metallocene are compounds of metals of groups IVb, Vb or VIb of the Periodic table, such as compounds of titanium, zirconium, hafnium, vanadium, Nidia, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium or titanium, and especially zirconium.

Metallocene of this type are known and described, for example, in the following works: 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-5017714 were obtained and Chem.342/1988/21.

Of particular interest are metallocene, especially zirconocene that contain the same derivatives as ligands.

Preferably they are the volumes;

R1and R2the same or different and are a hydrogen atom, a C1-C10alkyl group, a C1-C10-alkoxygroup, C6-C10-aryl group, a C6-C10-arroceros C2-C10-alkenylphenol group, C7-C40-arylalkyl group, C7-C40-alcylaryl group, C8-C40-arylalkylamines group, OH group or a halogen atom;

R3the same or different and represent a hydrogen atom, a halogen atom, a C1-C10is an alkyl group which may be gorodilova, C6-C10-aryl group, -NR2, -SR, - OSiR3, -SiR3or PR2where R is a halogen atom, a C1-C10is an alkyl group or a C6-C10-aryl group;

R4-R8have the meanings indicated for R3or adjacent radicals R3, R4, R5, R6, R7, R8can form an aromatic or aliphatic ring together with the United with them atoms;

R9is:

< / BR>
< / BR>
< / BR>
= BR10, = AIR10, -Ce-, -Sn-, -O-, -S-, = SO, =SO2, = NR10, =CO, =PR10, = P(O)R10or hydrogen,

where

R10and R11equal or razlicylas group, C6-C10-aryl group, a C6-C10- ftoruridina group, C1-C10-alkoxygroup, C2-C10-alkenylphenol group, C7-C40- arylalkyl group, C8-C40- arylalkylamines group or a C7-C40- alcylaryl group, or R10and R11in each case, together with the attached atoms to form a ring, and M2is silicon, germanium or tin.

Are also of interest 4,5,6,7 - tetrahydroindole analogs of compounds I.

In the formula I preferably

M1represents zirconium;

R1and R2the same and are methyl or chlorine, especially chlorine;

R3-R8represent hydrogen or C1-C4-alkyl;

R9matter

< / BR>
or

< / BR>
where

R10and R11the same or different and are C1-C4-alkyl or C6-C10-aryl. In particular, R10and R11the same or different and are stands or phenyl.

Ingenierie or tetrandrine ligands of the formula I preferably substituted in provisions 2-,2,4-,4,7-, 2,6-,2,4,6-, 2,5,6-, 2,4,5,6 or 2,4,6,7-especially in the 2,4,6 - position, preferably Camaseno the stands.

In addition, of particular interest are the compounds I in which the substituents in the 4 - and 5 - positions indanilnykh radicals /R5and R6/ with connected with him by the atoms form a benzene ring. Such systems with condensed cycles may also be substituted by the radicals specified for R3-R8. An example of compound I of this type can serve as dimethylselenide /2-methyl-4,5 besonderer/zirconiabased.

Metallocene formula I are especially suitable for obtaining high molecular weight polyolefins with high stereoregularity and high molecular weight.

Metallocene formula I and metallocene described in the preceding references, can be obtained, for example, in accordance with the following reaction scheme:

< / BR>
X= Cl, Br, 1, or 0-tosyl, H2Rcand H2Rdare ligands, for example,/substituted/indene.

* additional stage hydrogenation, for example, if Ingenierie ligands need to turn in the ligands tetrahydroindene.

Ways of getting in principle known from the literature: see Journal of Organometallic Chem 288/1985/ 63-67, EP-A-320762 and quoted relative links described in them metallocenes.

Connect four is 2
Rdsee the reaction scheme/. Some of these derivatives indeno known and commercially available. Indene with special substitution can be obtained the following ways:

a/ H2Rcand H2Rd=

< / BR>
Synthesis of conduct in accordance with references /or similar/:

J. Org. Chem 49/1984/ 4226-4237. J/Chem.Soc.Perkins II 1981, 403-408. J. Am. Chem. Soc. 106/1984/6702. J. Am. Soc. 65/1943/567, J. Med.Chem 3P/1987/ 1303-1308 and Chem. Weg.85/1952/ 78-85.

in/ H2Rcand H2Rd< / BR>
< / BR>
2,4-substituted indene H2Rcand H2Rdused as starting compounds can be obtained in two different ways: 1/ as the source connections use ketoaldehyde the formula shown in the reaction scheme below, the receipt of which is known /Synthesis 1985, 1058/.

The reaction ketoaldehyde with cyclopentadiene lead in an inert solvent in the presence of a base. Such alcohols as methanol, ethanol or tert-butanol, particularly methanol, are preferred.

As a basis you can use a wide range of compounds. Examples that can be specified are hydroxides of alkali and alkaline earth metals, alkoxides of alkali and alkaline earth metal amines. Preferred ethoxide sodium tert-piperonyl potassium and potassium hydroxide.

The molar ratio between the original compounds, including the reasons may vary within wide limits. Preferably the ratio of ketoaldehyde : cyclopentadiene : base = 1 : 1-1,5 : 2-3, especially 1 : 1,1 : 2,5

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

The duration of reaction usually varies from 10 minutes to 1000 hours, preferably from 1 to 30 hours.

The substituent in position 2 - you can enter in the Grignard reaction after the conversion of 4 - monosubstituted of indene, 4 - monosubstituted 2 - indanone General fashion /Organic Synthesis, CoII. Vo1, V, 1973, 647/. Subsequent removal of water results in, 2,4 - substituted indeno.

2,4 - substituted indene get as isomers on double bond, which can be used directly to obtain the corresponding metallocene complexes.

< / BR>
/ Another possible and profitable strategy includes the following scheme: 2 - substituted bentelhalal subjected to interaction with an appropriately substituted malonic fluids similar to the method known from the literature /J. Org.Chem became ways lead to disubstituted derivatives of propionic acid.

The reaction ring closure to obtain a 2,4 - disubstituted 1 - indanone are the usual ways /reaction Friedel-/ after the conversion of carboxylic acid in the carboxylic acid chloride.

The recovery of the ketone by known methods and subsequent exclusion of water gives 2,4 - disubstituted indeni.

s/ H2Rcand H2Rd=

< / BR>
Connection with H2Rcand H2R0get in the interaction of compound II

with compound III

< / BR>
or its anhydride in the presence of a catalyst of the Friedel -. In this formula, X1and X2are nucleophilic atmasamyama groups, such as, for example, halogen, hydroxyl group or tselnye groups, particularly bromine or chlorine.

Get indanone IV or IVa:

< / BR>
Depending on the designated substituent at the aromatic ring indanone receive in the form of two isomeric structures of formulas IV and IVa. You can restore them individually or in a mixture are known from the literature methods such reducing agents as NaBH4or Zi AlH4in appropriate indanol, and then degidratiruth with such acids as sulfuric, oxalic or a pair of toluensulfonate what minioxidil, silica gel or molecular sieves to obtain indeno formula V and Va, respectively /H2Rwith/H2Rd// Bu11. Soc. Chim.Fr.11 /1973/, 3092. Were obtained 9/1990/3098/

< / BR>
Examples of suitable catalysts for Friedel-can serve as AlCl3, AlBr3, FeCl3, SbCl5, SnCl4BF3, TiCl4, ZnCl2H2SO4, polyphosphoric acid, H3PO4or AlCl3/NaCl melt, especially AlCl3.

The initial compounds of formulas II and II are known and commercially available or can be obtained by methods known from the literature.

The reaction of lead in an inert solvent, preferably methylene chloride or CS2. If the original components are liquid, it is not necessary to use a solvent.

Molar ratio between the starting compounds, including the catalyst of the Friedel-may vary within wide limits. The molar ratio of compound II : III : catalyst preferably is 1 : 0.5 to 1.5 : 5, in particular 1 : 1 : 2,5-3.

The reaction temperature is preferably from 0 to 130oC, especially from 25 to 80oC.

The reaction time usually varies from 30 minutes to 100 hours, and preferably from 2 to 30 hours.

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

Substituted indene can be obtained as isomers on double bond /V/Va/. They can be cleaned by-products by distillation, through column chromatography or crystallization.

Based on indeno formula V and Va, which can be used in the form of mixtures of isomers, getting metallocene proceeds by methods known from the literature (see AU-A-31-478/89, J. were obtained Chem 342/1988/21 and EP-A-284707/ in accordance with the reaction scheme.

d/ H2Rcand H2Rd=

< / BR>
R12and R13have the meanings indicated for R4-R8.

These benzo-condensed indeno and their further transformation into metallocen 1 are in accordance with the reaction scheme below:

< / BR>
Derivatives of naphthalene of the formula A are commercially available or they can get well-known from the literature methods "Reaction Friedel-crafts and related" Willy, new York, 1964, T. 11, page 659-766, Bull.Soc.Chim Belges, 58 (1949), 87, J. Amer. Chem. Soc. 89 (1967)2411).

Transformation of compounds of formula C are the JV is rede, for example, in the ethanol solutions ethoxide sodium (J. Org. Chem 23(1958) 1441, J. Am. Chem. Soc. 70(1948)3569).

The compounds of formula C hydrolyzing ways known in the literature, using a hydroxide of alkali metal such as potassium hydroxide or sodium hydroxide, and decarboxylases methods known from the literature, thermolysis obtained dicarboxylic acid to obtain the compounds of formula D (J. Org. Chem. 23(1958)1441 & J. Am. Chem. Soc. 70(1948)3569).

Ring closure to obtain substituted benzoindole formula E are methods known from the literature, due to the interaction with such gloriously reagents, such as SOCl2to obtain the corresponding acid chlorides, followed by cyclization using the catalyst of the Friedel-in such an inert solvent, such as AlCl3or polyphosphoric acid in methylene chloride or CS2/ Organometallics 9(1990) 3098, BuII. Soc. Chem. Fr. 3(1967) and J. Org. Chem. 49(1984)4226).

The transformation of the derivatives of besondere formula C are the methods known from the literature, restoring using sodium borohydride or sociallyengaged in an inert solvent, such as, for example, diethyl ether or THF, or by alkylation using alkylaryl the alcohols in acidic conditions, such as, for example, using pair-toluensulfonate or oxalic acid, or when interacting with a dehydrating agent, such as magnesium sulfate or molecular sieves (Organometallics 9(1990)3098, Acta. Chem. Scand B. 30(1976)527 and J. Amer. Chem. Soc 65(1943)567).

Derivatives of besondere formula G can also be synthesized in 4 steps in another method of synthesis is not described in more detail below on the basis of substituted naftalina (Bull. Soc. Chim 3(1967)988).

Receiving systems ligands of the formula J and transformation into a bridge chiral metallocene formula K, and the target allocation racemic forms in principle known (AU-A-31478/89, J. were obtained. Chem 342(1988)21, EP 0 284707 and EP 0-320762). And finally, the derivative of besondere formula G deprotonated with strong bases, such as, for example utility, in an inert solvent, and subjected to interaction with the reagent of formula H to obtain a ligand system of the formula J. It then deprotonated with two equivalents of a strong base, such as utility, in an inert solvent, and subjected to the interaction with the corresponding tetrahalides metal, such as zirconium tetrachloride, in a suitable solvent. Suitable solvents are aliphatic and aromatherapynatural or diethyl ether, or halogenated hydrocarbons, such as methylene chloride. Racemic and metformi share the extraction or management, using suitable solvents.

To derive metallocene formula I are known from the literature methods, for example the interaction with such alkylating agents as, for example, motility (Organometallics 9(1990)1539, J. Amer. Chem. Soc. 95(1973 6283 and EP 0 277004).

The following compounds can be given as the examples metallocenes that can be used according to the method of the present invention:

bis(cyclopentadienyl)zirconiated, biscyclopentadienyl, biscyclopentadienyl, bis(cyclopentadienyl)benzylcyanide, bis)(cyclopentadienyl)bis- (trimethylsilyl)zirconium, 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

bis(pentamethylcyclopentadienyl)zirconiated,

bis(indenyl)zirconiated,

diphenylmethane,

dimethylsilane-1-tetrahydroxyphenylchlorin

dimethylsilane-1-(2-methyltetrahydrofuran)zirconiated,

dimethylsilane-1- (2,3,5,-trimethylcyclopentanone)zirconiated,

dimethylsilane-1-(2,4 - dimethylcyclopentane)zirconiated,

dimethylsilane-1-indenyltitanium,

dimethylsilane-1-interdimensional,

dimethylgermylene-1-indenyltitanium,

dimethylsilane-1-(2 - methylindenyl)zirconiated,

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

PHENYLMERCURIC-1-(2-methylindenyl)zirconiated, dimethylsilane-1-(2-methyl-4-ethylidene)zirconiated, ethylenebis-1-(4,7-dimethylindole)zirconiated,

phenyl(methyl)Silvis-1-indenyltitanium,

phenyl(vinyl)Silvis-1-indenyltitanium,

diphenylsilane-1-indenyltitanium,

dimethylsilane[1-(2-methyl-4 - tert.-butylidene)]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)] qi is-trimethylindium)] zirconiabased, methylpenicillin (2-methyl-4,6 - diisopropylphenol)zirconiated, 1,2-atanderson /2-methyl-4,6 - diisopropylidene/ zirconium - dichloride and dimethylsilane /2 - methyl-4,5-benzhydryl/zirconiabased.

Chiral metallocene preferably used in the form of a racemate upon receipt of the catalyst according to the invention. However, it is possible to use pure R - or S-shaped. Optically active polymer can be obtained by using these pure stereoisomeric forms. However, the meso-form metallocene should be allocated as active in the polymerization of the center (the metal atom) in these compounds is no longer chiral due to mirror symmetry at the Central metal atom, and she could not give any tactical polymer. If you do not separate the meso-form, atactic polymer will be formed along with isotactic and syndiotactic polymer. For some applications it may be desirable, for example, for soft moulding or receiving grades of polyethylene.

The catalyst on the carrier receive at a temperature between -20 and +120oC, preferably from 15 to 40oC, interaction of the catalytic component with A catalytic component B in such a way that nerator the Oh inert suspension medium, for example, n-decane, hexane, heptane or diesel oil with a solution of the catalytic component B, in an inert solvent, such as toluene, hexane, heptane or dichloromethane, or with fine solid catalytic component C. conversely, it is possible to carry out the reaction of a solution of the catalytic component B with the solid catalytic component A.

The reaction is carried out at intensive mixing, for example, when the mixing molar ratio Al/Zr between 100/1 1000/1 and, preferably, between 100/1 and 2000/1, and when the reaction time between 5 and 120 minutes, preferably between 10 and 30 minutes, in an inert conditions.

For the reaction time to obtain a catalyst to change the color of the reaction mixture, in particular when using metallocene with maximum absorption in the visible region, the progress of the reaction can be monitored by such changes color.

When the reaction time is exhausted, the supernatant is separated, e.g. by filtration or decantation, and the solid part which remains is washed with one to five times the inert suspension medium such as toluene, n-decane, hexane, diesel oil or dichloromethane. This operation of washing/extraction/ deletes the races is the soluble metallocene. Advantageously, but not necessarily, lead the whole reaction to the filter under pressure. It is also possible to use various inert solvents for flushing with an inert solid part. The filtrate and washing liquids are colorless, regardless of previously used metallocene.

Thus obtained catalyst can be dried in a vacuum to powder or re-suspended in suspension, in an inert suspendida environment, for example, heptane, hexane, diesel oil or dichloromethane, measured in the polymerization system.

Further, the present invention relates to a method for producing a polyolefin by polymerization or copolymerization of an olefin of the formula Ra-CH = CH-Rbwhere Raand Rbthe same or different, and are hydrogen atom or a hydrocarbon radical containing from 1 to 14 carbon atoms, or Raand Rbtogether with the atoms connecting them can form a ring, at a temperature of from -60o200oC at a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst, if the catalyst is the reaction product according to the method of the present invention.

The polymerization or Seki, in one or more stages at a temperature of from about -60 to 200oC, preferably from 30 to 80oC. Olefins of the formula Ra-CH=CH-Rbyou can polimerizuet or copolymerizate. In this formula, Raand Rbthe same or different and are hydrogen atom or alkyl radical containing from 1 to 14 carbon atoms. However, Raand Rbcan also together with the United with them atoms to form a ring. Examples of such olefins are ethylene, propylene, I-butene, I-hexene, 4-methyl-I-penten, I-octene, norbornene or such diolefin as norbornadiene, ethylidene-norbornene vinylnorbornene, Dicyclopentadiene and 1,4,5,8 - dimethano - 1,2,3,4,4 a, 5,8,8 a - octahydronaphthalene /DMON/. In particular, propylene and ethylene will polimerizuet or copolymerized, or get cycloolefinic polymer; if from 0.1 to 100 wt.% in relation to the total amount of monomer, of at least one monomer of the formulae I, II, III, IV, V or VI.

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
where

R1, R2, R3, R4, R5, R6, R7,and R8the same or different and are a hydrogen atom, or a C1-C8alkyl radical, and perhaps for the same radicals in the various formulae to have is rmula VII:

< / BR>
where

n is an integer from 2 to 10,

from 0 to 99 wt.% in relation to the total amount of monomers, at least one acyclic olefin of the formula VIII

< / BR>
where R9, R10, R11and R12the same or different and are hydrogen or C1-C8is an alkyl radical subjected to polymerization.

If you want to add hydrogen as molecular weight regulator and/or increase activity. The total pressure in the polymerization system is from 0.5 to 100 bar. Polymerization, preferably, are in the most convenient for the industry range from 5 to 64 bar.

The catalyst according to the method of the present invention is preferably used in a concentration, based on the transition metal, from about 10-3up to 10-8mole, preferably from 10-4up to 10-7mol, of transition metal per DM3solvent or DM3volume of the reactor.

If the polymerization are as polymerization in suspension or in solution, usually an inert solvent, which is usually used for processes Ziegler low pressure. For example, the way leading to aliphatic or zikali the Academy of Sciences and methylcyclohexane.

It is possible to continue to use gasoline or hydrogenated fractions of diesel oil. You can also use toluene.

If an inert solvent, the monomers introduced in gaseous or liquid form.

Polymerization can last as long as is desirable, since the catalyst used in the method of the present invention shows only a slight dependence of the reduction of the activity of the polymerization time.

Before the catalyst is introduced into the reactor, another connection alkylamine, for example trimethylaluminum, triethylaluminum, triisobutylaluminum or triisopropanolamine can optionally be added to the polymerization system in a concentration of from 2 to 0.001 mmole A1 / kg of the contents of the reactor to make the polymerization system inert (for example to remove catalyst poisons present in the olefin/.

However, it is not necessary to use additional substances for the catalysis of the polymerization reaction, that is, the catalyst according to the method of the present invention and is preferably, can be used as the sole catalyst for polymerization of olefin.

Molecular weight recip is a multi-stage process, or use more than one metallocene that makes it possible to obtain polymers with a broad molecular weight distribution.

In addition, the attainable molecular weight polymer with a solid catalyst according to the method of the present invention is determined by the type of used metallocene, a compound of aluminum and a molecular ratio of aluminum and metallocene.

The method of the present invention/the catalyst of the present invention/ mainly characterized in that the polymerization preventing the formation of undesirable deposits in the reactor. Another advantage of this method is the complete absence of aromatic solvents and easy way to obtain a catalyst.

According to the method of the present invention it is possible to obtain polymers which have a very narrow molecular weight distribution /Min/Mhfrom about 2 to 10, especially from 2 to 4.

Examples.

All glass equipment is heated in vacuum and rinsed with argon. All operations are in the flask Slence with exclusion of moisture and oxygen. The solvents used in each case are fresh over Na /K alloy in nitrogen atmosphere and stored in splavleniya /heating rate: 10oC/min/.

To obtain a catalytic component A design steel explosion-proof reactor system pump 60 bar of inert casinosites, the temperature control system due to a cooled jacket and the second cooling circuit via a heat exchanger on the pumping system. The pump system pumps out the contents of the reactor by a pump through a line from the bottom of the reactor, and supplies it to the mixer and back into the reactor through the line of ascent through the heat exchanger. The mixer is designed in such a way that due to the tapering of the cross section of the tube creates an increased flow rate of the raw material in the zone of turbulence, which provides a thin raw line in the axial direction and opposite to the direction of flow, through which a certain amount of water in each case can be submitted to cycles with argon under a pressure of 40 bar. The reaction is monitored using the sampler is installed in the circuit of the pump.

However, in principle, possible to use other reactors are described, for example, in DE 3731665 and DE 4004477. The racemic dimethylsilane-1/2-methylidene/-zirconiabased synthesized according to the methods DE-A-4035883 and DEIA 4035886. Metallocen diphenylmethylene-9 - forensic cyclopentadienyl-sironidae synthesized as described in J. Am. Chem. Soc, 110/1988/ 6255. The racemic metallocene dimethylsilane-1-/2-methyl-4,5-benzhydryl/ zirconiabased synthesized as described previously (see the formula K/.

Aluminum was determined after hydrolysis using water and sulfuric acid using complexometric titration according to the method of Shwarzenbach. Trimethylaluminum supplies in the form of pure compounds S CHERING AG. Soluble in toluene methylalumoxane get for the comparative examples in the form of a 10% by weight solution in toluene from S CHERIN'G AG and, accordingly, for the determination of aluminium, contains 36 mg A1 /ml. The average degree of oligomerization, a certain reduction of the freezing point in benzene is h = 20.

Example 1

Obtaining a catalytic component A

5 DM3does not contain aromatics diesel oil /etc boiling point 100-120oC/ injected into the reactor with stirring volume 16 DM3in inert conditions. Add 0,5 DM3the trimethylaluminum /5,2 mol/ and temperature withstand 25oC. In the reactor serves 200 g Aerosi1 /R/ 812 /Dedussa AG/ pre-dried at 120oC in the fluidized bed with argon, through a measuring hopper for solid product, and homogenized suspension with the help of a mixer and system nakagawara by supplying argon gas and the reaction support 10 bar through the release valve. After adding the total amount of water system pump off and stirring is continued for another 5 hours at 25oC.

A solid component of catalyst A obtained in this way are used in the form of 12% by weight suspension in diesel oil /etc boiling point 100-120oC/. The content of aluminum is 1.06 mmole A1 per ml of suspension. Selected solid part contains 31 wt.% A1. This suspension medium contains less than 0.1 wt.% aluminum.

Example 2

5 ml of the suspension of catalyst component A from example 1 is introduced into G3 of the Frits Slanka in the atmosphere of argon and filtered. The hard part, which remains, re-suspended in 20 ml containing no aromatic inert diesel oil /etc boiling point 100-120oC/, 0,5 mol 1/500 molar solution of biscyclopentadienyl in absolute toluene is metered into this suspension, and the mixture was stirred for 15 minutes at 30oC. the resulting mixture was sequentially filtered, and the solid residue washed with 20 ml of diesel oil and again suspended in 20 ml of diesel oil for polymerization.

Polymerization

Dry tubular reactor is blown with nitrogen to remove oxygen, and filled with 0.9 DM3inert di is eribaum 70oC, and the suspension of the catalyst is metered into the reactor at a pressure of 7 bar of ethylene without the introduction of additional activator. After 2 hours the reactor pressure dropped, and the resulting polymer is filtered from the suspension and dried for 12 hours in a vacuum dryer. Get 23 grams of polyethylene powder with a bulk density 0,175 kg/DM3and viscosity 392 cm3/year In the reactor is not visible deposits on the walls and stirrer. Molecular weight distribution /according to GPC/ is Min/Mh= 2,6.

Comparative example 1

Repeat the polymerization of example 2 with the difference that is used as a catalyst 0,029 mg biscyclopentadienyl dissolved in 10% by weight in the solution methylalumoxane in toluene /12 mmol A1/. Otherwise identical conditions obtain 40 g of polyethylene with a viscosity of 380 cm3/g bulk density to 0.060 kg/DM3. When the reactor is opened, it is found that the solid sediment thickness of 1 mm on the wall and stirrer.

Comparative example 2

Repeat the polymerization of example 2, with the difference that a mixture of 20 ml of the suspension of the catalytic components A from example 1 with 0.5 ml of a 1/500 molar solution biscyclopentadienyl 407 cm3/g and a bulk density 0,067 kg/DM3. When opening the reactor wall and the stirrer find solid sediment thickness of 0.2 mm

Example 3

Obtaining the catalyst of example 2 is repeated, with the difference that use 800 ml suspension of catalytic components A from example 1 and 11.7 mg biscyclopentadienyl dissolved in toluene. 160 DM3the reactor, which was previously doing inert, serves 80 l of diesel oil /boiling point 100-120oC/ and heated to 50oC, and introduce an ethylene pressure of 3 bar. The catalyst is injected through the tube transfer, and the pressure of ethylene is increased up to 7 bar, and the temperature remain constant at 70oC upon cooling. After 3 hours of polymerization, the reactor pressure dropped, the suspension is filtered on a filter under pressure. After drying in a vacuum dryer receive 4.3 kg of polyethylene, corresponding to the reduced time of contact with the release of 5.1 kg/mmol. hour bar/ with a bulk density of 140 g/DM3. In the reactor is not visible deposits on the wall or stirrer. The resulting product has a density 0,953 g/cm3viscosity 463 cm3/g molecular weight distribution /according to GPC/ Min/Mh=2,5.

Printnum hexane instead of diesel oil so boiling 100 - 120oC/. Then the catalyst was dried for 2 hours at a pressure of 10-3mbar and a temperature of 30oC to obtain free presuposes powder. The analysis shows 27 wt.% Al and 40 million shares.

1250 mg of dry catalyst is mixed with 80 g of polystyrene powder, which was previously doing inert, as the mixing means, and the polymerization is carried out in the reactor of 1.5 DM3with a propeller stirrer for 1 hour at 70oC and a pressure of 4 bar ethylene. The reactor pressure dropped, and the powder is removed and extracted with boiling toluene. After drying in vacuum remains 29 g of polyethylene with a viscosity of 420 cm3/,

Example 5

30 mg diphenylmethylene-9-fertilitylinfertility dissolve in a small amount of toluene, and mixed with 60 ml suspension of catalytic components A from example 1 in the Frit Slanka. After 15 minutes the solution is filtered and the filter cake washed with diesel oil, and then re-suspended in 20 ml of diesel oil.

Polymerization

The reactor is blown dry with nitrogen /volume of reactor 16 DM3/ and fill 10 DM3propylene and heated to 30oC. After 15 minutes, the slurry catalyst having measured the Roux in the reactor was raised to the polymerization temperature 50oC at a rate of 10oC/min by supplying additional heat, and then maintain this temperature by cooling. After 1 hour of polymerization finish it by adding isopropanol, the reactor pressure dropped, the reactor opened. The walls of the reactor and the stirrer is completely free from precipitation. After vacuum drying of the product get 0,56 kg free presuposes powder with a viscosity of 3450 cm3/g and so melting /DSK/ 11,2oC. the Average particle diameter d50according to the sifting is 600 μm.

Comparative example 3

To obtain a catalyst of 9.4 mg diphenylmethylene-9-fertilitylinfertility dissolve 20 cm3toluene solution methylalumoxane /corresponds to 27 mmol Al/, and is subjected to interaction with methylalumoxane when aged for 15 minutes. In parallel, a dry reactor volume 16 DM3purge with nitrogen and filled with 10 DM3liquid propene. 30 cm3solution in toluene methylalumoxane added to the reactor, and the mixture was stirred at 30oC for 15 minutes. The solution of the catalyst is sequentially injected into the reactor, and the polymerization system was heated to the polymerization temperature 50oC/103/g, MW= 4,97106g/mol, Min/Mh= 2.2 and melting point /DSK/ is 134,1oC. the Average particle diameter d50according to the analysis sifting is 2500 microns.

Example 6

Polymerization leads by the method of example 5, with the difference that a 4.9 mg of the racemic dimetallic-2-methyl-1-interchangealbe subjected to interaction with 60 ml suspension of catalytic components A of example 1, and polymerization is carried out at 70oC. After opening the reactor precipitation is not detected. Vacuum drying of the product gives 0.35 kg polymer with a viscosity of 170 cm3/g, and so boil /DSK/ of 142.8oC. the Average particle diameter d50free perelevayuschimsya powder according to the analysis sifting is 1000 microns and a fines content /less than 100 microns/ 0.8 wt.%.

Comparative example 4

According to the method of comparative example 3 with the difference that use 5.2 mg of racemic dimethylsilane-1-/2-methylindenyl/zirconiabased, the polymerization is carried out at the Noah drying of the product is obtained 1.3 kg of polypropylene having a viscosity 151 cm3/g and melting point /DSK/ 145oC. the Average particle diameter d50according to the analysis sifting is 350 μm.

Example 7

1 mg of isopropylidene-9-fertilitylinfertility, dissolved in toluene, add in/to 40 ml of a suspension of solid catalyst component A from example 1, and the resulting mixture is stirred for 30 minutes. In parallel, 1.5 l reactor rinsed with ethylene and filled with 600 cm385% by weight solution of norbornene in toluene and 20 ml of a suspension of solid catalytic component A of example 1, the resulting mixture was successively stirred at 70oC for 30 minutes and saturated with ethylene under a pressure of 6 bar. After adding the catalyst, the resulting mixture will polimerizuet for 1 hour at 70oC, and maintain a constant pressure at 6 bar by sequential feeding of ethylene. The reactor pressure dropped, the solution is stirred for 30 minutes and with 10 cm3water and filtered. A clear solution was added dropwise to 5 DM3acetone, the resulting mixture is stirred for 10 minutes, and precipitated precipitated polymer is filtered and washed with acetone. After drying at 80oC in a vacuum dryer obtain 32 g of a copolymer with Vya is Repeat the polymerization according to the method of example 7, with the difference that 40 cm3suspension of solid catalytic component A of example 1 replaces 20 cm310% by weight solution of MAO in toluene. Obtain 15.7 g of a copolymer with a viscosity of 86 cm3/g and a glass transition temperature Tg156oC.

Example 8

Repeat the polymerization of example 7, with the difference that instead of 1 mg isopropylidene-9-fertilitylinfertility use 5 mg diphenylmethylene-9-fertilitylinfertility, which is mixed with a catalytic component a of example 1, and polymerization is carried out at a pressure of 3 bar of ethylene and 40oC. Obtain 24 g of a copolymer with a viscosity of 367 cm3/g and a glass transition temperature Tg176oC.

Comparative example 6

Repeat the polymerization of example 8, with the difference that 40 cm3suspension of solid catalytic component A of example 1 is replaced by 20 cm310% by weight solution of MAO in toluene. Get a 8.9 g of a copolymer with a viscosity of 187 cm3/,

Example 9

Obtaining the catalytic components (A:

Repeating the reaction of example 1, with the difference that diesel oil substitute in 6 DM3n-decane and 200 g Aerosi R 812 /Degussa AG/ replace on 200 g of silica gel CD 3216-30 /GRACE AG/. Specification of the about BET the media is 310 m2/, similarly dosed 72 g of water in the resulting suspension.

The thus obtained solid catalyst component A is used in the form of a 10% by weight suspension in n-decane. The content of aluminum is 0.96 mmole Al mol suspension. Selected solid part contains 28 wt.% Al. The suspension medium contains 0.1 wt.% aluminum.

Example 10

40 ml of a suspension of solid catalytic component A of example 3 is filtered off with suction in the Frit Slinka and re-suspended in diesel oil /so boiling 100 - 120oC/ 1.9 mg of racemic dimethylsilane-/2-methyl-4,5-benzhydryl/zirconiabased dissolved in 5 ml of toluene, the resulting solution is mixed with the suspension and the resulting mixture was filtered after 15 minutes. The filter cake sequentially washed with a small quantity of diesel oil and re-suspended in 5 ml of diesel oil.

Polymerization

Polymerization leads by the method of example 5. However, adding a suspension of the catalyst before adding to the reactor 15 ml of 20% by weight solution of triisobutylaluminum in diesel oil. Vacuum drying of the product gives 0.27 kg free presuposes polypropylene powder with a viscosity of 380 cm3/g ml suspension of solid catalytic components A of example 9 was filtered with suction in the Frit Slanka, and re-suspended in diesel oil /so boiling 100 - 120oC/ a 20.3 mg of the racemic dimethylsilane-2-methylindenyl/zirconiabased dissolved in 10 ml of toluene, the resulting solution is mixed with the suspension and the resulting mixture was filtered after 15 minutes. The filter cake was washed with a small amount of diesel oil, and re-suspended in 10 ml of diesel oil.

Polymerization

70 DM3the reactor is purged with dry nitrogen fill 40 DM3propylene and heated to 30oC, then add 60 ml of 20% by weight solution of triisobutylaluminum in diesel oil. After 15 minutes, the slurry catalyst is injected through the valve. The internal temperature of the reactor was raised to 70oC with a speed of 2oC/min and then maintained at this temperature for 2 hours by cooling. The reaction is completed by adding isopropanol. The product is dried in vacuum to obtain 8.2 kg free presuposes polypropylene powder with a viscosity of 160 cm3/the Average particle diameter d50is 550 μm, and the fines content /less than 100 μm/ data analysis sifting 1.5 wt.%.

Example 12

6.2 ml of a suspension of catalytic component A and an example is l not containing aromatics diesel oil /100 - 120oC. T. boiling/ 0.25 ml 1/500 molar solution of biscyclopentadienyl in absolute toluene measure in this suspension, and the mixture was stirred at 30oC for 1/4 hour. The resulting mixture was sequentially filtered, and a solid portion that remains, washed with 2 ml of diesel oil, and re-suspended in 20 ml of diesel oil for polymerization.

Polymerization

Polymerization leads by the method of example 2. 19 g of polyethylene powder with a bulk density 0,160 kg/DM3and a viscosity of 265 cm3/g receive. In the reactor is not visible deposits on the walls and stirrer. Molecular weight distribution /GPC/ Min/Mh=2,6

Example 13

Obtaining the catalytic components A:3

5 DM3n-decane injected into 16 DM3the reactor with stirring under inert conditions, 0,50 DM3the trimethylaluminum /5,2 mol/ add, and the temperature is maintained at 25oC. In the reactor introduced 200 g of silica gel CD 3216-20 /GRACE AG/ pre-dried at 130oC in vacuum /10-2mbar/ in 24 hours and measure in the reactor through a hopper for solids and homogeneous suspended with the help of a mixer and pumping system. Volatile part of siliquae 1 wt.% during the drying process. BET surface of the media is 310 m2/the Average particle size is 25 Mm, and pore volume /H2O/ 1.6 cm2/, Only 78 g of water in portions of 0.1 ml at intervals of 15 seconds is metered into this mixture for 3.25 hours. The pressure is increased at the expense of the injected argon gases and reaction, maintain a constant at 10 bar through the valve, increasing the pressure. After adding the entire amount of water, the pumping system is disconnected, the stirring is continued for another 5 hours at 25oC.

The solid catalytic component A, thus obtained, is used in the form of 13.2% by weight suspension in n-decane. The content of aluminum is of 1.46 mmole Al mol suspension. Selected solid product containing 30 wt.% Al. The suspension medium contains less than 0.1 wt.% aluminum.

Example 14

13 cm3suspension of solid catalytic components A of example 13 is filtered off with suction in the Frit Slanka, and re-suspended in diesel oil /so boiling 100 - 120oC/ a 3.3 g of the racemic dimethylsilane-/2-methyl-4,6-diisopropylidene/zirconiabased dissolved in 5 cm3toluene, the resulting solution is mixed with the suspension and the resulting mixture was filtered after 15 minutes. The filter is cm3diesel oil.

Polymerization

16 DM3the reactor is purged with dry nitrogen, injected 10 DM3propylene and heated to 30oC. In the reactor is injected 3 ml of pure triisobutylaluminum. After 15 minutes, the suspension of catalyst introduced into the reactor through the gate. After the start of polymerization, the temperature inside the reactor increased to the polymerization temperature of 70oC at a rate of 10oC/min, summing up additional heat, and then maintaining this temperature by cooling. After 1 hour of polymerization her stop, adding isopropanol - reactor pressure dropped, and the reactor opened.

On the walls of the reactor and the stirrer is absolutely no sludge. In the vacuum drying of the product is obtained 0.4 kg free presuposes polypropylene powder with a viscosity 324 cm3/g, melting point /DSK/ 143oC and srednevekovym molecular weight Min=431000. Molecular weight distribution /according to GPC/ is Min/Mh=2,6. The flow rate of melt /230oC/ /5 kg/ MFP is=3,4 DG/min. Average particle diameter d50free presuposes powder according to the analysis sifting is 200 μm.

Comparative example 7

the options A of example 13 is replaced by 20 cm310% by weight solution of MAO in toluene /30 mmol Al/, and 3 cm3triisobutylaluminum in the reactor is replaced by 8 cm3the same solution of MAO. Otherwise identical conditions receive 0.9 kg of propylene with a viscosity of 260 cm3/g and so melting /DSK/ 143oC and molecular weight /srednevekovym/ Min=297000. Molecular weight distribution /according to GPC /Min/Mh=2,3. When the reactor is open, becomes visible continuous sediment thickness of 3 mm on the walls and stirrer.

Example 15

15 cm3suspension of solid catalytic component A of example 13 is filtered off with suction in the Frit Slanka, and re-suspended in diesel oil /so boiling 100 - 120oC/ 3 mg of the racemic dimethylsilane-/2-methyl-4,5-benzhydryl/zirconiabased dissolved in 5 cm3toluene, the resulting solution is mixed with the suspension and the resulting mixture was filtered after 15 minutes. The filter cake sequentially washed with a small quantity of diesel oil and re-suspended in 10 cm3diesel oil.

Polymerization

The polymerization are by way of example 14. After vacuum drying of the product is obtained 1.3 kg free presuposes polypropylene powder is nowym molecular weight Min=347000. Molecular weight distribution /according to GPC/ is Min/Mh=2.5 to about

1. The catalyst for polymerization of olefins on the media containing the product of the interaction alyuminiiorganicheskikh connection to media (a) and metallocene component (B), characterized in that it contains alyuminiiorganicheskikh connection to media (A) obtained by reacting at least one alyuminiiorganicheskikh connection with dry media under inert conditions with subsequent hydrolysis of the resulting suspension by adding water.

2. The polymerization catalyst under item 1, characterized in that as alyuminiiorganicheskikh compounds it contains alkylamine compound of General formula AIRR1R2where R, R1and R2may be the same or different and denote C1-C6is an alkyl group, a C1-C6-alkyl fluoride group, a C6-C18-aryl group, a C6-C18-porarily group or hydrogen.

3. The polymerization catalyst under item 1, characterized in that it contains alkylamine compound of General formula AIRR1R2where R, R1and R2may be the same or different and hereafter is I, what it contains as alkylamines connection trimethylaluminum.

5. The polymerization catalyst under item 1, characterized in that it contains as a carrier of an oxide of silicon or aluminum.

6. The polymerization catalyst under item 1, characterized in that it contains the carrier in the amount of less than 0.1 kg per mol alkylamine.

7. The polymerization catalyst under item 1, wherein the metallocene component is metallocenes or mixture metallocenes.

8 the polymerization Catalyst under item 1, wherein the metallocene component is zirconocenes.

9. The method of producing catalyst for polymerization of olefins on the media through the interaction of a metallocene component and suspension alyuminiiorganicheskikh compounds on the carrier, characterized in that alyuminiiorganicheskikh connection on the media produced by the interaction of at least one alyuminiiorganicheskikh connection with dry media under inert conditions with subsequent hydrolysis of the resulting suspension by adding water.

10. The method of producing polyolefin by polymerization or copolymerization of an olefin of the General formula Rand-CH=CH-Rbwhere th radical, or Randand Rbtogether with the United with them atoms may form a ring, at a temperature of from -60 to 200oC and a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase in the presence of a polymerization catalyst containing the product of the interaction alyuminiiorganicheskikh connection on the media and metallocene component, characterized in that alyuminiiorganicheskikh connection is produced by the interaction of at least one alyuminiiorganicheskikh connection with dry media under inert conditions with subsequent hydrolysis of the resulting suspension by adding water.

11. The method according to p. 10, characterized in that will polimerizuet or copolymerized ethylene or propylene.

 

Same patents:

The invention relates to a method for producing alpha-olefins of high molecular weight polymers in solution by polymerization of ethylene or mixtures of ethylene and at least one higher olefin C3-C12in the presence of a coordination catalyst, consisting of two components: the first contains Ti, Mg, Al, and the second mixture alkylamine and alkoxyalkane, when heated to 180-320oC, and the formation of the first and second catalyst components and their mixing is carried out in the stream at a temperature lower than the 30oC

The invention relates to a spherical solid components of catalysts for the polymerization of olefins, comprising deposited on dihalogenide magnesium in an activated form of a compound of titanium, containing at least one link with a titanium halide and one OR group with the specified group OR is linked to an atom of titanium in such quantities that the molar ratio OR/Ti is greater than or equal to 0.5

The invention relates to a catalytic system comprising the transition metal compounds of groups IV-B of the Periodic table of elements and activator, as well as to the composition using this catalytic system for obtaining polyolefins, in particular polyethylene, polypropylene and copolymers of ethylene -- olefin

The invention relates to a method of producing catalyst type catalyst of the Ziegler-Natta having granular media

The invention relates to a catalytic system used for the stereospecific polymerization of alpha-olefins, in particular propylene and polypropylene obtained in the presence of catalytic systems

The invention relates to a catalyst on the carrier for the polymerization of olefins, the method of its production and the use of such catalyst in the polymerization of olefins

The invention relates to a method of gas-phase polymerization of olefins of the formula CH2= СНR, where R is hydrogen, alkyl or aryl with 1 to 8 carbon atoms

The invention relates to a component of the catalyst or catalyst, which is suitable for use in the reaction stereoregular polymerization or copolymerization of alpha-olefins and particularly relates to a magnesium-containing, titanium containing catalyst component on the substrate or catalyst suitable for receiving homopolymer or copolymer of alpha-olefin

The invention relates to the components of the catalyst, the way they are received and catalysts for polymerization of olefins of General formula CH2= CHR

The invention relates to a method for producing polymers and copolymers of olefins CH2=CHR, where R is a hydrogen atom or an alkyl radical having from 1 to 10 carbon atoms that includes at least one phase (co)polymerization in the gas phase in the presence of a highly active catalyst, obtained from compounds of titanium with a magnesium halide in active form as a carrier and alkyl aluminum compounds

The invention relates to a method of determining the stable operating range of the gas polymerization in the fluidized bed by using a condensing options

The invention relates to a method for producing alpha-olefins of high molecular weight polymers in solution by polymerization of ethylene or mixtures of ethylene and at least one higher olefin C3-C12in the presence of a coordination catalyst, consisting of two components: the first contains Ti, Mg, Al, and the second mixture alkylamine and alkoxyalkane, when heated to 180-320oC, and the formation of the first and second catalyst components and their mixing is carried out in the stream at a temperature lower than the 30oC

-olefins of high molecular weight polymers in solution" target="_blank">

The invention relates to the production of-olefins of high molecular weight polymers in solution by the interaction of ethylene or mixtures of ethylene and higher C3-C12alpha-olefin - catalyst prepared using alkyl compounds of magnesium, aluminum, tert-butyl chloride, the compounds of Ti, alcohol and inert hydrocarbon solvent thus prepared catalyst using different methods (a) and (b), and the formation and mixing of the catalyst components is carried out in a stream at a temperature below 30oC

The invention relates to a spherical solid components of catalysts for the polymerization of olefins, comprising deposited on dihalogenide magnesium in an activated form of a compound of titanium, containing at least one link with a titanium halide and one OR group with the specified group OR is linked to an atom of titanium in such quantities that the molar ratio OR/Ti is greater than or equal to 0.5

FIELD: polymerization catalysts.

SUBSTANCE: invention describes metallocene catalytic component of catalytic system for production of polyolefin with isotactic or syndiotactic/isotactic block structure with length of monomer unit up to C10, said component having general formula R"(CpR1R2R3)(Cp'R1R2')MQ2, where Cp represents cyclopentadienyl ring substituted by at least one substituent; Cp' is substituted fluorenyl ring; R" structural bridge imparting steric rigidity; R1 optional substituent in cyclopentadienyl ring located at a distance to bridge and including a bulky group XR*3 wherein X is selected from group IVA elements and R*, the same or different, are hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms; R2 optional substituent in cyclopentadienyl ring, nearest to bridge and not vicinal to remote substituent, which substituent has formula YR# wherein Y is selected from group IVA elements and R#, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R3 optional substituent in cyclopentadienyl ring, nearest to bridge and being hydrogen or having formula ZR$ wherein Z is selected from group IVA elements and Rs, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R1' and R2' are independent substituents in fluorenyl ring, one of them having formula AR3’’’ wherein A is selected from group IVA elements and each of R’’’ represents independently hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms and the other being hydrogen or second group AR3’’’; M is transition metal from group IVB or vanadium and each Q is either hydrocarbon radical with 1-20 carbon atoms or halogen.

EFFECT: enabled preparation isotactic or syndiotactic/isotactic block polymer with length of monomer unit up to C10.

30 cl, 13 dwg, 2 tbl, 10 ex

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