Component of the catalyst, the catalyst for polymerization of olefins, a method of obtaining a catalytic component and method for the polymerization of olefins

 

(57) Abstract:

The invention relates to a component and catalyst for polymerization of olefins. Describes a component of a catalyst for polymerization of olefins CH2= CHR, where R is hydrogen or C1- C10is alkyl containing carrier - magnesium halide and applied to it the product of the interaction: (1) a titanium compound containing at least one link Ti-OR1where R1- lower alkyl; (2) the solid product resulting from decomposition (the formation of magnesium halide or product containing the magnesium halide complex of the formula MgX2nAlR11X12pAlX3(A), where X is chlorine or bromine; X1is chlorine, bromine or alkoxy group; R11is alkyl containing C1- C20; n = 1-6; p is from 0 to 1; (n+p)= 1-6, inclusive, characterized in that the carrier has a spherical shape and porosity (defined by the mercury method) of more than 0.5 cm3/, the Method of obtaining a catalytic component under item 1 or 2, namely, that the spherical carrier impregnated with a hydrocarbon solution of the titanium compounds (1), and then subjected to reaction with a complex of (A). Describes also the catalyst for polymerizes the above component and Al-Akilova connection; and the method of polymerization of olefin using the above catalyst. The advantage of this invention lies in the fact that the obtained new components of the catalyst can be used for gas-phase polymerization of ethylene and its mixtures with olefins and which allow to obtain polymers with relatively narrow molecular weight distribution and uniform distribution of the comonomers in the polymer chain. 4 C. and 14 C.p. f-crystals.

The present invention relates to components and catalysts for the polymerization of olefins, in particular, polymerization of ethylene and mixtures thereof with alpha-olefins CH2=CHR, where R is a hydrocarbon radical having 1-10 carbon atoms.

There are catalysts used for the polymerization of mixtures of ethylene and alpha-olefins, and which are capable of producing LLDPE with a relatively narrow molecular weight distribution, as well as the ability to uniform distribution of co monomer in the polymer chain.

Examples of catalysts of this type are described in U.S. patent 4 089 808, where the solid component of catalyst is obtained by decomposition of the adducts MgCl2nAlRX12pAlX3with Ti-, V - iligal XnMg(OR)2-nor RMgX, with titanium compounds containing at least two Ti-OR connection, and with halogenation agents.

In the above-mentioned patents the possibility of fixing the catalyst components in an inert carriers, such as silicon dioxide and aluminum oxide. However, these catalysts are not suitable for polymerization in the gas phase, because they do not possess the necessary morphological characteristics and/or produce polymers with properties such as, for example, bulk density, which does not allow gas-phase processes. These gas-phase processes in the fluidized bed used for producing HDPE and LLDPE, are increasingly used in industrial production.

Therefore, of particular interest are the catalysts which are suitable for use in gas-phase processes, which allow to obtain polymers with the desired properties.

Below describes the components of the catalysts, which have been detected, can be used for gas-phase polymerization of ethylene and mixtures thereof with alpha-olefins, and which allow, with Polesov in the polymer chain.

The components of the present invention, applied to dihalogenide magnesium in spherical form having a porosity (determined by the mercury method, described below), more than 0.5 cm3/g, include the reaction product of:

(I) a titanium compound containing at least one bond selected from the "Ti-halogen" and "Ti-OR1"where R1is a hydrocarbon radical with 1-12 carbon atoms, or the group COR; with

(II) a solid product obtained by decomposition with the formation of dihalogenide magnesium or product containing dihalogenide magnesium) complex having the formula

MgX2nAlR11X12nR1OH (where X is halogen, and R1is a hydrocarbon radical containing 1-12 carbon atoms), with such number of moles of alcohol that at room temperature it is a solid, and at temperatures of about 100-130oC - liquid. Typically, n ranges from 2 to 6.

In the case when R1represents ethyl, propyl or butyl, then the number of moles of alcohol, preferably equal to 3.

From dihalogenide magnesium, used as a carrier, it is preferable MgCl3.

Dealcoholization sterilizating adduc the olo 1 M, by heating at a temperature increasing from about 50oC to about 150oC, and when processing a stream of nitrogen, after which dealcoholizing adduct again subjected to heat treatment up until the alcohol content in it will not be reduced to 0.1 to 0.3 to 1 M dihalogenide magnesium.

Alternative steroidogenic adduct containing about 1M of alcohol, is subjected to reaction with compounds capable of decomposing the adduct by reaction with the OH group of the alcohol until the alcohol is nearly or even completely separated from the adduct.

Examples of reactive compounds are ORGANOMETALLIC compounds of elements of groups I-III of the Periodic system, and halogenated compounds of Si and Sn. In particular, such compounds can be A1-alkali, for example, A1-trialkyl and A1-dialkylamide, SiCl4and SnCl4.

Methods of obtaining steroidogenic adducts described, for example, in U.S. patents 4 469 648; 5 100 849 and 4 829 034, which are introduced in the present description by reference.

Operating conditions for thermal and chemical dealcoholization described in U.S. patent 4 399 054 and applications Europatent EP-A-553805 and EP-A-553806 that are introduced in the present description postradiotherapy solution of titanium compound (1), and then subjected to reaction with a complex of (A) dissolved in an excessive amount A1-dialkylated; alternative media is first treated with a solution of complex (A), and then the solid product is subjected to reaction with the titanium compound (1).

Titanium compounds (1) having the formula XnTi(OR1)y-npreferred are such compounds in which X is a halogen; R1represents a hydrocarbon radical with 1-12 carbon atoms, or COR-group; y is the valence of titanium, and n is number from 0 to y, inclusive.

Typical halogenated titanium compounds having the above formula are: TiCl4, TiBr4, TiCl3, Ti(O-n-C3H7)2Cl2, TiCl3OCH3, Ti(O-n-C4H9)Cl3, Ti(O-n-C4H9)2Cl2.

Titanium compounds belonging to the above type and which does not contain halogen, are compounds of the formula Ti(OR)4where R is a hydrocarbon radical with 1-12 carbon atoms. Among the titanium compounds containing no halogen, preferred are Ti(O-n-C3H7)4, Ti(O-n-C4H9)4and Ti(OC6H5

Titanium compounds (1), such as Ti-amides and karboksilirovanie titanium compounds can be used, for example, Ti[N(C2H5)2)Cl3, Ti[N(C6H5)2]Cl3, Ti(OOC-C6H5)Cl3.

Titanium compounds can also be used in a mixture with vanadium or zirconium compounds.

Among the complexes (A) having the formula MgX2nAlRX12pAlX3preferred are compounds in which X and X1are chlorine, and R11is a hydrocarbon radical containing 1-10 carbon atoms; especially preferred are MgCl22,5 Al(i-C4H9)Cl2, MgCl21,5 Al(h-C4H9)Cl2and MgCl22Al-EtCl2.

The decomposition of the complex (A) with the formation of dihalogenide magnesium or products containing dihalogenide magnesium, carried out by reaction of the complex (A) with itself titanium compound (1) at a temperature of from -10oC to 140oC, and preferably from 0oC to 50oC, in the presence of an inert hydrocarbon diluent; or by dissolving compl, after application of this complex to the halide of magnesium it is subjected to reaction with gaseous anhydrous hydrochloric acid or with an ORGANOMETALLIC compound of an element of groups I-III of the Periodic system, such as Al-trialkyl; or with aliphatic or cycloaliphatic alcohol.

Methods of obtaining the specified complex and its decomposition with the formation of dihalogenide magnesium or products containing dihalogenide magnesium, described in patents US 4 089 808 and 4 472 520 laid in the present description as analogues.

For polymers with narrow molecular mass distribution (MMD) and/or elastomeric copolymers of alpha-olefins, acquiring elastomeric properties after vulcanization, in the solid component of catalyst, it is desirable to introduce electron-donating compound selected, for example, from ethers, esters, amines, ketones and silicon compounds.

In particular, donors inner electrons can be, for example, ethers, such as dialkylamide or arylalkyl esters; and complex alkilany, cycloalkenyl and arrowy esters of carboxylic acids.

In particular, specific primarily esters can serve as ethyl acetate, cyclohexylacetate, methyl-p-toluate, ethyl-p-anizat, and esters of phthalic and maleic acids, such as n-butylphthalate, di-isobutylphthalate, di-n-octylphthalate, etc.

Examples of silicon compounds containing at least one OR group are methyl-cyclohexyl-dimethoxy-silane, diphenylmethylsilane, methyl-t-butyl-di-ethoxysilane.

Preferably, the compound used as an internal donor of electrons present in a molar ratio of electron donor/Mo," which is from 0.05:1 to 1:1.

The components of the present invention together with A1-alkylamine compounds, in particular, with A1-trialkylamine, such as A1-trimethyl, A1-triethyl, A1-triisobutyl, A1-tri-n-butyl-forming catalysts with high activity or polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical having 1-10 carbon atoms.

If you need to obtain olefin polymers and copolymers with narrow MMD, the catalysts of the present invention, in addition to the solid component and A1-alilovic components may also contain electron-donor compound (internal donor electrons). In the catalysts used delsie, at least one nitrogen atom, such as 2,2,6,6-tetramethylpiperidine, N-methyl-2,2,6,6-tetramethylpiperidine, tetramethylguanidine, tetramethylguanidine, 2,2-dimethylhydroxylamine, A1-diethyl-2,2,6,6-tetramethylpiperidine, and organic NITRILES, such as, for example, benzonitrile and anisometry, are particularly suitable as external donors.

Other examples of compounds that can be used as donors of external electrons are silicon compounds containing at least one Si-OR bond described earlier.

Donors of external electrons are used in a molar ratio electron donor/magnesium", which is typically between 0.1 and 10 and preferably between 0.5 and 2.

As mentioned above, these catalysts are particularly suitable for use in the polymerization of ethylene and mixtures thereof with alpha-olefins with obtaining linear polyethylene of low density or linear polyethylene, very low density (LLDPE and LEONP) or elastomeric copolymers with a lower content of diene (EPA and EPDM).

The catalysts, which include the connection-internal donor of electrons and connection-generalagent, in particular, TiCl4can also be used for the stereospecific polymerization of alpha-olefins, in particular propylene.

The catalysts of the present invention are particularly suitable for the implementation of the gas-phase polymerization, because of its morphological stability, they allow to obtain the polymer in a spherical shape, thereby giving these polymers valuable properties, such as high bulk density.

The preferred method of performing the polymerization in the gas phase is described in International patent application WO92/21706 and in the patent application Italy M192-A-000589, the description of which is introduced into the present description by reference. The methods described in these applications include preliminary contact of the catalyst components, preliminary polymerization, and the stage vapor-phase polymerization in one or more reactors arranged in series one after the other, in a fluidized or mechanically hang out layer.

The following examples are presented for purposes of illustration, and should not be construed as limiting the present invention.

These properties were determined by immersing a known quantity of sample in a known amount of mercury in dilatometer with subsequent gradual hydraulic pressure increase of mercury up to 2000 kg/see Introduction pressure mercury into the pores depends on the diameter of the pores. The measurements were carried out using the device for determining porosity "Porosimeter 2000 series" (Carlo Erba). Based on the reduction of mercury and quantities supplied pressure was determined porosity, pore distribution and surface area.

The particle size of the catalyst was determined by the method based on diffraction of light emitted by the optical laser with a monochromatic pulse (with the use of device "Malvern Instrum. 2600").

MIE melt index: ASTM-D 1238.

MIF melt index: ASTM-D 1238.

Fluidity: defined as the time in which 100 g of the polymer flows through the funnel, the diameter of the hole which is 1.25 cm, and its walls inclined to the vertical axis 20o.

Bulk density: D1N - 53194.

The morphology and particle size distribution of polymer particles: ASTM-D 1921-63.

The fraction soluble in xylene, was determined at 25oC.

The content of the co monomer: mass percentage content of co monomer was determined by IR spectrometry.

True density: ASTM-D 792.

Example 1. Obtaining spherical media (adduct MgCl2/EtOH).

Specified adduct with 3M alcohol and having an average size of approximately 60 μm, was subjected to heat treatment at a temperature in the range from 50 to 150oC as long, until it reaches the partial dealcoholisation with Poluchenie to 130oC up until the amount of residual alcohol will not amount to about 10% by weight.

Obtaining complex (A).

In a glass 350 cm3the vessel, equipped with a mechanical stirrer, and feed stream of anhydrous nitrogen was introduced to 57.2 g EACH (ethyl-A1-dichloride); 4.5 g AlCl3and 9.5 anhydrous MgCl2.

The suspension was heated to 120oC and kept at this temperature for 5 h, resulting in the obtained homogeneous solution, after cooling to 90oC planted 15 cm3of toluene. The liquid obtained after cooling to room temperature, maintained their stability and transparency.

Obtaining a solid component.

In a glass 750-cm3a reactor equipped with a mechanical stirrer, was administered to 58 g of spherical carrier obtained according to the procedure described previously. Then, stirring at room temperature, was introduced 120 cm3hexane, 58 cm3Ti(OBu)4and 11 cm3anisole. Under these conditions, the mixture was kept stirring during 30 min, after which the temperature was lowered to 0oC for 3 h gave the solution obtained previously complex (A).

The resulting suspension was heated ASS="ptx2">

After cooling to 50oC, the suspension decantation, and the liquid phase was removed by siphonaria. The obtained solid product is washed eight times the same volume of hexane at room temperature, and then exposed for 3 h in a vacuum drying at 50oC. as a result of chemical analysis were obtained the following data, wt.%:

Ti (total) is 7.85

Ti111- 6,75

Mg - 14,15

Al - 0,75

Cl - 54,85

BuOH - 11,0

EtOH - 4,0

The anisole - 2,8

Polymerization of ethylene (HDPE).

2.5-liter autoclave, degassed for 2 hours at 70oC in a stream of nitrogen was introduced 900 cm3hexane containing 0.5 g of Al three-isobutyl and 0,0203 g of the above-described spherical component, suspended in 100 cm3n-hexane. The resulting mixture was stirred, heated to 85oC, and then applied ethylene (6,3 bar) and hydrogen (4,7 bar), the polymerization was carried out for 3 hours, and during this period of time ethylene was applied so as to maintain constant pressure. After 3 hours the reaction was stopped by rapid release of ethylene and hydrogen. This has resulted in 385 g of polymer having the following characteristics:

MIE - 3.7 g/10 min

MIF/MIE - 29

Morphology SUB>=CHR, where R is hydrogen or C1-C10is alkyl containing carrier - magnesium halide and the applied product interaction:

(1) a titanium compound containing at least one link Ti-OR1where R1is lower alkyl; with

(2) the solid product resulting from decomposition with the formation of magnesium halide or product containing the magnesium halide complex of the formula

MgX2nAlR11X122,5 Al(i-C4H9)Cl2, MgCl22AlEtCl2and MgCl21,5 Al(n-C4H9)Cl2. 7. Component under item 2, characterized in that it includes an electron-donating compound.

8. Component under item 7, characterized in that the electron-donating compound selected from the group consisting of ethers and alilovic, cycloalkyl and ariovich esters of aromatic carboxylic acids.

9. Component under item 8, characterized in that the electron-donating compound selected from di-n-octylphthalate.

10. Component under item 9, characterized in that the electron-donating compound selected from silicon compounds containing at least one OR group.

11. Component under item 2, characterized in that the carrier is obtained by deal dnim radical, having 1 to 12 carbon atoms, and n is an integer from 2 to 6.

12. Component on p. 11, wherein R1selected from ethyl, propyl and butyl.

13. The method for the catalytic component under item 1 or 2, characterized in that the spherical carrier impregnated with a hydrocarbon solution of the titanium compounds (1), and then subjected to reaction with a complex of (A).

14. The method according to p. 13, characterized in that the complex (A) is dissolved in an excessive amount A1-dialkylated.

15. The method according to p. 1 or 2, characterized in that the carrier is treated with a solution of complex (A), and then subjected to reaction with the titanium compound (1).

16. The catalyst for polymerization of olefins CH2=CHR, where R is H or alkyl containing 1 to 10 carbon atoms, characterized in that it includes components on PP.1 - 12, and A1-Akilova connection.

17. The catalyst according to p. 16, characterized in that A1-alkylbis connection is A1-trialkyl.

18. The method of polymerization of olefin CH2=CHR, where R is H, or C1-C10-alkyl, with the use of a catalyst, wherein the catalyst used is a catalyst for PP.16 - 17.

 

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