Component of the catalyst for polymerization of olefins, process for its production and a catalyst for polymerization of olefins

 

(57) Abstract:

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 obtained catalysts have high activity and allow you to obtain copolymers having a low content of diene and a very low crystallinity. Components they are applied on digalog magnesium, having specified characteristics, the compounds of a transition metal selected from Ti, V, Zr, Hf, and the compound contains at least one arenas. 4 C. and 16 h.p. f-crystals, 2 tab.

The present invention relates to a catalyst component and catalyst for polymerization of olefins, the use of these catalysts for the polymerization of olefins, in particular ethylene and its mixtures with olefins of General formula CH2= CHR, where R is a hydrocarbon radical having 1 to 10 carbon atoms.

Component of the catalyst according to the invention contains a transition metal compound containing at least one arene (aromatic hydrocarbon), and the specified connection is applied to the halide of magnesium, which has the prescribed values of specific surface and porosity.

Connected is teratory. Usually, these compounds have the General formula M(aryl)2where M is a metal (usually V or Ti) having a valence of 0, and arenas is usually benzene or toluene, or a General formula M (arenas)Al2Cl8where M is typically Ti or Zr has a valency of 2.

Examples of catalysts of this type are described in patents FR 2338077, BE 867495, GB 2035338 and GB 2096122. These catalysts, in addition, giving a polymer with a relatively low output, do not have the morphological characteristics suitable for the operating conditions of the modern processes of gas-phase polymerization. In particular, FR 2338077 describes the components of the catalyst obtained by applying (durene). TiAl2Cl8or Ti (toluene)2anhydrous MgCl2activated by grinding. Thus obtained components are used together with Elektrodinamika compounds and Al-alkyl compound for polymerization of polypropylene. Output in the polymerization process is always very low, the Ti content in the polymer is always > about 15 parts per thousand, and the resulting polymer has always lowest stereoregularity.

Low yield in the polymerization also obtained by polymerization of ethylene. Examples of homopolymerization of ethylene and copolymerization with 1-hexene of Pokedex melt, indicate relatively low molecular weight.

In addition, the above-described catalysts are not suitable for gas-phase polymerization, as they do not possess morphological characteristics and yield polymers having properties such as bulk density, is not suitable for gas-phase processes.

Now it has been found that the application of transition metal compounds containing arenas, magnesium halides, having the specified characteristics, it is possible to obtain catalysts with high activity when used for the polymerization of olefins.

In particular, the components of the catalyst according to the invention and containing catalysts allow to obtain copolymers of ethylene, optionally with a low content of diene, having a very low crystallinity.

Component of the catalyst according to the invention includes a compound of a transition metal selected from Ti, V, Zr and Hf containing at least one arenas, and deposited on a magnesium halide with at least one of the following characteristics:

(I) a specific surface area of > 300 m2/g (by BET method);

(II) the porosity according to the method of mercurimetric > 0.5 cm3/,

the displaced or unsubstituted benzene ring. Examples of suitable arenes include: benzene, toluene, naphthalene, xylene, trimethylbenzene, trivinylbenzene, tetraisopropyl, hexamethylbenzene and chlorobenzene and tetramethylbenzene. In the compounds of metal containing arena, the metal associated with arena - links.

The porosity according to the method of mercurimetric is determined according to the method described below.

Diploid magnesium can be successfully used in the form of spherical particles having a size in the range of 5 to 150 μm; the spherical particles of mean those particles for which the ratio between the major axis and the minor axis of 1.5, and preferably, 1,3.

From halides of magnesium, it is preferable MgCl2. Preferably, the specific surface area has a value of from 300 to 900 m2/g and porosity method mercurimetric, preferably, ranges from 0.8 to 2.2 cm3/,

Dihalide magnesium, used as substrates, obtained by partial or complete removal of the alcohol from adducts of the General formula MgX2nR1OH, where X is halogen, R1- C1-12is a hydrocarbon radical, and n is a number from 2 to 6. R1is ethyl, propyl or butyl, the number of moles of alcohol is preferably 3.

Removing alcohol from the adduct you what agrevanie at a temperature increasing from about 50oC to approximately 150oC in a stream of nitrogen, from the adduct then remove the alcohol next, all the while the heat up until the alcohol content reaches of 0.05 to 0.3 mol per mol of dihalide magnesium.

Alternatively, the adduct of General formula MgX2nR1OH, or adduct, which has been partially removed alcohol to a residual alcohol content of about 1 mol can interact with the compounds capable of decomposing the adduct reaction with OH group of the alcohol until the alcohol is completely removed from the adduct. Examples of the reaction compounds are ORGANOMETALLIC compounds of elements from I to III group of the Periodic table and halogenated Si - and Sn - compounds. In particular, can be specified Al-alkali, for example, Al-trialkyl and Al-dialkylamide, SiCl4and SnCl4.

Ways of getting adducts described, for example, in U.S. Patents NN 4469648, 5100849 and 4829034.

Working conditions of thermal and chemical removal of the alcohols described in the Patent US 4399054 and in the application EP-A-553805 and the application EP-A-553806. In particular, the implementation of the patent US 4399054 get the magnesium halides, with specific surface area of >300 m2/,

Examples of compounds 2(A)

where

M is a transition metal selected from Ti, V, Zr and Hf, has a valence of 0.

Preferably arena is benzene, toluene, xylene, trimethylbenzene, tetraisopropyl, tetramethylbenzene, hexamethylbenzene or chlorobenzene.

These compounds can be obtained, for example, by the methods described in Journal of Chimical Society Chem. Comm., 1973, pages 866 - 867, and in applications EP-A-398402 and EP-A-437897. Examples of these compounds are Ti (benzene)2, Ti (toluene)2, Zr (benzene)2, Zr (toluene)2V (mesitylene)2.

The transition metal may also have a valence other than 0; examples of these transition metal compounds containing arenas, are compounds having the General formula

M1(arenas)Al2X8-nRvn(B)

where

X is halogen, M1Is Ti, Zr or Hf, RV- alkyl radical having 1 to 4 carbon atoms, and n is a number from 0 to 4.

Among the compounds having General formula (B), preferred are those in which M1Is Ti, X is chlorine, RVis ethyl or methyl, and n is a number from 0 to 2. Examples of these compounds are (arenas)TiAl2Cl8, (arenas)TiAl2Br8, (arenas)TiAl2CI8, (arenas)TiAl2Cl6Et3, (arenas)TiAl2Cl3

The direction of synthesis of these compounds is the same as described in Z. Naturforsch B, volume 10 (1955), page 665.

Additional examples of compounds of transition metals used in the components of the invention are vanadium compounds having a General formula

V(arenas)2AlX4(C)

where

X is halogen, arenas - benzene, toluene, xylene, trimethylbenzene, trivinylbenzene, tetraisopropyl, tetramethylbenzene, hexamethylbenzene or chlorobenzene.

The components of the catalyst according to the invention can be obtained by contacting compounds of the transition metal halide of magnesium in a solvent selected from aromatic hydrocarbons and halogenated hydrocarbons, at temperatures from 0 to 100oC and over a period of time from 15 minutes to 4 hours.

The alternative to this method of obtaining lies in the interaction of the transition metal with TiCl4according to the method described in patent US 4987111. The reaction can take place before, during, and after application of the compound of the transition metal halide of magnesium. Thus obtained components are particularly suitable for the tsya for stereospecific polymerization of olefins, such as propylene, 1-butene, 4-methyl-1-Pantin, it is suitable for introduction into a solid component of catalyst of electron-donor compound (internal donor), we choose, for example, from ethers, esters, amines, ketones and compounds of silicon. In particular, the connection with the internal electrondensity may be selected from ethers and alkyl, cyclonic and aryl-esters of polycarboxylic acids, such as, for example, esters of phthalic and maleic acid, in particular ad-butylphthalate, diisobutylphthalate, di-ad-octylphthalate.

Other predominantly used electron-donor compounds are 1,3-diesters of General formula:

< / BR>
where

RII= RIIIor RIIRIIIand RII, RIII- C1-18-alkyl, C3-18-cycloalkyl, C6-18aryl radicals;

RIV=RVor RIVRVand RIV, RV- C1-4-alkyl-radicals.

Connection with internal electrondensity usually present in a molar ratio with magnesium from 1 to 4 to 1 to 20.

The components of the invention react with alumoklyuchevskite compounds, for example, A1-alkylsilanes, in particular, A1-trialkylamine, such as, for example, A1-trimerisation olefins of General formula CH2=CHR, where R is hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms. Other suitable alumoklyuchevskite compounds are alumoxane connections that are linear, branched or cyclic compounds containing at least one group of the General formula (E):

< / BR>
where

RVIthe substituents are the same or different and are-O-Al(RVI)2group, or RIIDeputy, where RII-C1-18-alkyl, C3-18-cycloalkyl, C6-18the aryl radical and, optionally, some of the RVIthe substituents may be a halogen atom.

In particular, alumoxane connections that can be used in the method of the present invention are linear alumoxane represented by General formula (F):

< / BR>
where

n is an integer from 0 to 40,

and cyclic alumoxane represented by the General formula (G):

< / BR>
where

n is an integer from 2 to 40.

In formulas (F) and (G) RVIas defined above, preferably is C1-4is a hydrocarbon group and, more preferably, methylpropoxy or isobutyl group. Non-restrictive examples alumoxane-compounds suitable for the method for the case of stereoregular polymerization - olefins, upon receipt of the catalyst is also used electron-donating compound - external donor, which can be used in the presence or in the absence of the outer electrondonor. In contrast to what usually happens with catalysts Natta-Ziegler, with the components of the invention it is really possible to obtain polymers having a high index of stereoregularity without the use of external electron-donor compounds.

The external donor is preferably selected from Milanovich compounds containing at least one Si-OR bond, having the General formula RII4-nSi(ORIV)nwhere RII- C1-18-alkyl, C3-18-cycloalkyl, C6-18-aryl radical, RIV-C1-4-alkyl radical, and n is a number from 0 to 4. Examples of these silanes are phenyltriethoxysilane, diphenylmethylsilane, methylcyclohexylamine, methyl-tert.-butyl-dimethoxysilane, dicyclopentadienyliron.

1,3-diesters having the previously described formula, can also be successfully used as external donors.

As previously shown, the components of the catalyst according to the invention and the catalysts containing them, primenewswire and elastomeric terpolymers of ethylene with propylene and a lower content of diene, having a mass content units, derivatives of ethylene, from about 30 to 70%.

Polymerization of olefins in the presence of catalysts containing components of the catalyst according to the invention can be performed by known techniques, either in liquid or in gas phase using, for example, known techniques and fluidized layer or in conditions where the polymer is mixed mechanically.

The following examples are given to illustrate the invention but are not limiting it.

These characteristics are determined by the following methods:

the porosity and specific surface area by nitrogen: is determined by the BET method (Bruner, Emmett and teller) (used to install SORPTOMATIC 1990, Carlo Erba):

the porosity and specific surface of mercury: (mercurymedia): definition of immersion realized during many years of the sample in a known amount of mercury in the dilatometer and then hydraulic gradually increase pressure mercury up to 2000 kg/cm2. The pressure at which mercury enters the pores depends on the diameter of the pores. The measurement is performed using porosimetry "Porosimeter 2000 series, Carlo Erba. According to reduce the amount of mercury and the values used pressure Russ the interest content of the co monomer is determined by IR-spectroscopy;

the crystallinity by x-ray diffraction analysis.

Examples.

The basic methodology.

The receiving substrate.

Adduct of magnesium chloride and alcohol was obtained following the method described in example 1 of US patent 4399054. Adduct containing about 3 mol of alcohol, was suspended in 80 cm3anhydrous H.-heptane in a glass reactor with a capacity of 500 cm3. While maintaining a temperature in the range of 0 to 5oC under stirring for 1 hour was added 215 cm30,85-molar H.-heptane solution of triethylaluminum. Everything was heated up to 80oC, and the suspension was maintained at this temperature for 2 hours. The mixture was then filtered, and the solid precipitate was washed 5 times with 120 cm3heptane at 80oC. After drying at 45oC under vacuum was obtained MgCl2in the form of spherical particles having a specific surface area of 840 m2/,

Receiving (benzene)TiAl2Cl8< / BR>
46,74 g AlCl3(0,350 mol), 3.94 g of metallic Al (0,294 mol) and 250 cm3benzene was loaded in a nitrogen atmosphere in the flask with a capacity of 1 liter With stirring, the suspension was heated to the boiling point of benzene, and then was added dropwise a solution, provided the pressure, and was selected solid purple substance.

Receiving (arenas) TiAl2Cl8< / BR>
Compounds of transition metals containing arena, were obtained by the reaction of the exchange of ligands in accordance with the following method. In a flask with a capacity of 250 cm3was loaded in a nitrogen atmosphere of 5.45 mol (benzene) TiAl2Cl8dissolved in 80 cm3benzene, was added at 20oC 13 moles of new arene ligand, then all reacted for 1.5 hours. Formed precipitate was filtered, washed H.-hexane and dried under vacuum. The interaction of benzene and the arena was confirmed by gas chromatography (GC).

Application (arenas) TiAl2Cl8on MgCl2< / BR>
1,9 g MgCl2obtained as previously described, and 0.4 g (arenas) TiAl2Cl8dissolved in 30 cm3benzene, were loaded into a flask with a capacity of 100 cm3with a round bottom in a nitrogen atmosphere. The reaction was carried out at 80oC for 2 hours, and the solid was filtered by filtration and washed H.-hexane.

Example 1.

Polymerization of ethylene.

Was used component of catalyst obtained by applying (benzene) TiAl2Cl8on MgCl3anhydrous heptane. Then added 5 moles of triisobutylaluminum and the mixture was heated at 70oC. To maintain the pressure constant during the polymerization with the present supply of ethylene was supplied to the hydrogen at 5 MPa and ethylene at 8 MPa. After 3 hours the polymerization was terminated, the polymer was filtered and dried. Received 500 g of the polymer having a characteristic viscosity (measured in tetrahydronaphthalene at 135oC) equal 1,94.

Example 2.

Was repeated in example 1 using the catalyst component obtained by applying (naphthalene) TiAl2Cl8(obtained by the reaction of the ligands in accordance with the General procedure described previously) MgCl2. Received 230 g of the polymer having a characteristic viscosity of 1.88.

Example 3 - 6

A series of experiments by copolymerization of ethylene with propylene was carried out using the catalyst components obtained by the application of MgCl2compounds of General formula (arenas) TiAl2Cl8. Obtaining catalyst components was performed in accordance with the previously described General method. The polymerization conditions described below.

A common way copolymerization C2/C33propylene and ethylene to a total pressure of 13.3 MPa. After that was injected slurry containing a solid component of catalyst and 5 moles of triisobutylaluminum. Polymerization was performed at 20oC for 1 hour with a continuous flow of ethylene to maintain the pressure constant. Unreacted monomers were then unloaded, and the polymer was recovered and dried. Table 1 shows the arena present in the compounds of metals, as well as characteristics of the polymers that have been received.

Examples 7 to 9

Using components obtained by the application of MgCl2compounds of General formula (arenas) TiAl2Cl2was performed a number of experiments on terpolymerization of ethylene with propylene and butadiene. Obtaining catalyst components is carried out according to previously described methods. The conditions of polymerization are described.

A common way of terpolymerization C2/C3-butadiene

In a steel autoclave with a capacity of 2000 cm3equipped with a mixer and cooled at a constant temperature of 20oC, was the introduction of 650 cm3propylene and 60 g of butadiene; ethylene was introduced up until the total pressure reached to 11.8 MPa. Then it 5 mmol A1-triisobutyl. Polymerization was carried out at 20oC for 1 hour while continuously feeding ethylene to maintain the pressure constant. After completion of the polymerization, unreacted monomers were extracted, and the polymer was removed and dried under vacuum. Table 2 presents the arena present in the compounds of metals, as well as characteristics of the polymers that have been received.

Examples 10 to 11.

Two experiments on the polymerization of propylene were carried out in liquid monomer with the use of the solid component of the product, which was obtained by applying (benzene)TiAl2Cl8on MgCl2in accordance with the previously described General method. The test was carried out in a 2 l autoclave filled with 1000 cm3propylene; then were added to the solid component, 5 moles of triethylaluminum and electron-donor compound (external donor) in an amount corresponding to a molar ratio Al : donor = 20. When used as an electron-donating compounds of phenyltriethoxysilane was obtained a polymer having an index of stereoregularity equal 92,2 and characteristices viscosity, equal to 1.75. The output amounted to 10 kg of polypropylene per 1 g of solid component 500,000 g/g Ti). When used in coregulatory, equal br93.1, and characteristic viscosity equal to 1.50. The output was 12 kg of polypropylene per 1 g of solid component (600,000 g/g Ti).

1. Component of the catalyst for polymerization of olefins having the General formula

CH2= CHR,

where R is hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms,

containing a compound of a transition metal selected from the group consisting of Ti, V, Zr and Hf containing at least arenas and deposited on a magnesium halide, wherein the halogen to magnesium is at least one of the following characteristics:

(I) a specific surface area of > 300 m2/g

(II) porosity, specific method mercurimetric, > 0.5 cm3/,

2. Component p. 1, wherein the magnesium halide is MgCl2having a specific surface area of from 300 to 900 m2/g, spherical morphology and particle size of from 5 to 150 μm.

3. Component p. 1, wherein the magnesium halide is MgCl2having a porosity of from 0.8 to 2.2 cm3/g, spherical morphology and particle size of from 5 to 150 μm.

4. Component under item 1, characterized in that arenas is selected from the group consisting of benzene, toluene, xylene, trimethylbenzene, Trifan the NT under item 1, characterized in that the compound of the transition metal containing at least one arenas, has one of the following General formula:

M (arenas)2(A)

where M is Ti, V, Zr or Hf and has a valence of 0,

M1(arenas) Al2X8-nRyn(B)

where X is halogen;

M' is Ti, Zr or Hf;

RV- C1-C4-alkyl; n is a number from 0 to 4,

V (arenas)2AlX4(WITH)

where X is halogen.

6. Component under item 5, characterized in that the arenas selected from the group of benzene, toluene, xylene, trimethylbenzene, trivinylbenzene, tetraisopropyl, tetramethylbenzene, hexamethylbenzene, chlorobenzene and X is chlorine.

7. Component p. 1, wherein the magnesium halide is the product of the removal of alcohol from spherical products having General formula

MgX2n R OH,

where X is halogen;

R'- C1-C12is a hydrocarbon radical;

n is a number from 2 to 6.

8. Component under item 7, wherein the magnesium halide is MgCl2.

9. Component under item 1, characterized in that it further contains an electron-donor compound (internal donor).

10. The method of producing a component of a catalyst under item 1, characterized in that the halide of magnesium usaasa of aromatic hydrocarbons, halogenated hydrocarbons and mixtures thereof.

11. The method according to p. 10, characterized in that the compound of the transition metal interacts with TiCl4before , during or after contact with the halide of magnesium.

12. The catalyst for polymerization of olefins of General formula

CH2= CHR,

where R is hydrogen or a hydrocarbon radical C1-C10,

characterized in that it contains a reaction product between a component of the catalyst according to PP.1 - 9 of claims and alumoorganic connection.

13. The catalyst according to p. 12, characterized in that alumoorganic connection is trialkylaluminium.

14. The catalyst according to p. 12, characterized in that alumoorganic connection is alumoxane.

15. The catalyst according to p. 12, characterized in that it further contains an electron-donor compound (external donor).

16. The method of polymerization of one or more olefins having the General formula

CH2= CHR,

where R is hydrogen or a hydrocarbon radical C1-C10,

wherein the used catalyst containing component of the catalyst according to PP.1 - 9 claims.

17. The method according to p. 16, characterized in that primout polymers of ethylene and copolymers of ethylene, containing up to 20% -olefin having from 3 to 12 carbon atoms.

19. The method according to PP.16 and 17, characterized in that the receive elastomeric copolymers of ethylene with a-olefins having from 3 to 12 carbon atoms, optionally up to 10 mol.% diene, and these copolymers contain from 20 to 80 mol.% units of ethylene.

20. The method according to PP.16 and 17, characterized in that the receiving crystalline polymers of propylene and copolymers of propylene containing up to 20 mol.% ethylene and/or olefin having from 4 to 12 carbon atoms, and apply the catalyst p. 15.

 

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