The method of (co)polymerization of olefins

 

(57) Abstract:

Describes a multi-stage method for the polymerization of one or more olefins of the formula CH2=HR, where R represents hydrogen or alkyl, cycloalkyl or aryl group with 1-10 carbon atoms, characterized in that it includes a first stage of polymerization in which to obtain the olefin Homo - or copolymer will polimerizuet one or more of these olefins in one or more reactors in the presence of a catalyst containing reaction product between alkylamine compound and a solid component comprising a compound of the transition metal MIselected from the group consisting of titanium and vanadium, which do not contain links MIand the magnesium halide in active form; (C) the machining stage, during which the product obtained in the first stage of polymerization (A) in any way (a) is brought into contact with a compound capable of deactivating the catalyst, is present at this stage (A) and (b) is brought into contact with the compound of the transition metal M selected from the group consisting of titanium, zirconium, vanadium, or hafnium containing at least one connection M with optional alkylamines connection, and more reactors in the presence of the product, obtained at this stage of processing (In). The technical result - the creation of a method of obtaining a wide range of compositions of olefin polymer. 3 S. and 21 C.p. f-crystals, 2 tab.

The invention relates to a multistage process for the polymerization of olefins of the formula CH2= CHR where R is hydrogen or alkyl, cycloalkyl or aryl group with 1-10 carbon atoms), carried out in two or more reactors. In at least one reactor, one or more of these olefins are polymerized in the presence of a catalyst comprising the reaction product alkylamino connection connection Ti and/or V, deposited on a substrate from a magnesium halide in active form; thus receive olefinic polymer. The deactivation of the catalytic system, which operated in the first reactor, at least one other reactor one or more of the above olefins CH2=CHR polymerized in the presence of the product obtained by bringing into contact the specified olefin polymer with the compound of the transition metal M containing at least one connection M- , new polymer compositions obtained directly from these reactors.

Multistage processes p is t of particular interest for practical applications. The possibility of independent variation in any of the reactors of such process parameters as temperature, pressure, type and concentration of monomers, the concentration of hydrogen or other molecular weight regulator, provides significantly more flexibility in the control of the composition and properties of the final product one-step process

Usually multistage processes are using the same catalyst at different stages/reactors; the product obtained in a single reactor, unload and go directly to the next stage/reactor without changing the nature of the catalyst.

Multistage processes are used, for example, upon receipt of olefinic (co)polymers with a broad molecular weight distribution by cooking in different reactors mixtures of polymers with different molecular weight. The molecular weight of the final product in each reactor, and hence the range of its molecular weight distribution is usually controlled by using different concentrations of the molecular weight regulator, preferably hydrogen. Multistage processes used in obtaining high impact propylene copolymers by the sequential polymerization of propylmalonate ethylene and/or olefin, having 4-10 carbon atoms, while receiving stereoregular polymer; at the second stage, a mixture of ethylene and propylene will polimerizuet in the presence of the polymer containing the catalyst obtained in the first stage, you get a polypropylene compositions with improved impact strength.

Processes of this type are described, for example, in USP 4521566. In this patent the polypropylene compositions with high impact strength gain of the multistage process that includes at least one stage of homopolymerization propylene and at least one phase polymerization of ethylene/propylene mixtures, and these stages is carried out in the presence of a catalyst containing a compound of titanium deposited on a substrate of magnesium halide in active form.

In European patent application EP-A-433989 described the process of obtaining a polypropylene composition containing from 20 to 99% by weight of crystalline (co)polymer (the content by weight of Monomeric propylene units is at least 95%) and from 1 to 80% by weight non-crystalline ethylene/propylene copolymer (the content by weight of Monomeric ethylene units is from 20 to 90%). This process is carried out in two stages: in the first stage, about uglevodorodnom solvent, get a non-crystalline ethylene/propylene copolymer. At both these stages use the same catalyst containing a chiral metallocene or alumoxane.

In European patent application EP-A-433990 described two-stage process of obtaining a polymer composition based on propylene, similar to the process described in EP-A-433989, where in the first stage, carried out in liquid propylene, receive a specified crystalline (co)polymer of propylene, and the second stage gas phase polymerization receive non-crystalline ethylene/propylene copolymer. In this case also, the same catalyst containing a chiral metallocene or alumoxane use in both reactors.

In the German patent application DE 4130429 described multistage process of obtaining copolymers carried out entirely in the gas phase. In the first stage is obtaining a matrix containing Homo - or copolymer of propylene in an amount of from 45 to 95% by weight of the weight of the total product; in the second stage, carried out in the presence of previously obtained polypropylene matrix and a used catalyst, receive the ethylene/-olefin copolymer containing from 0.1 to 79.9% by weight of the Monomeric telenovellu carried out in the gas phase, using the same metallocene catalyst.

These processes have different limitations, one of which is caused by the fact that the same catalyst is used at different stages of the process, and therefore the characteristics of the products obtained at each stage, it is not always optimal. For example, heterophase copolymers obtained by a multi-stage method using titanium catalysts have low properties kauchukopodobnoe copolymer obtained in the second stage. Indeed, it is known that using titanium catalysts receive an ethylene/propylene copolymers containing relatively long sequences of the same monomer unit, and therefore, the elastomeric properties of the obtained product are low.

Currently found multistage process by which, using at different stages of this process, various catalytic systems, you can get a wide range of compositions of olefin polymer. In particular, the process according to the present invention includes a first stage, on which the olefin polymer in the presence of a titanium or vanadium catalysts, the second stage, which inactivate the catalyst, when is inane transition metal M, selected from Ti, Zr, V or Hf containing at least one link with M - and/or products of their interaction, will polimerizuet one or more olefins, and these olefins are the same or different from olefins, polymerized in the first stage.

The process of the present invention differs in that it includes:

(A) the first stage of polymerization where to get olefin Homo - or copolymer, polimerizuet one or more of the above olefins CH2=CHR in one or more reactors in the presence of a catalyst containing reaction product between alkylamine compound and a solid component comprising a compound of the transition metal MIselected from Ti and V, not containing links M-, and magnesium halide in active form;

(C) the stage of processing at which the product obtained in the first stage of polymerization (A), in any way

a) is brought into contact with a compound capable of deactivating the catalyst, is present at this stage (A); and

b) bring into contact with the compound of the transition metal M selected from Ti, Zr, V or Hf containing at least one communication M and, optionally, with alkylamines connection.

(C) second stage of polymerization, in which the scientists at this stage of processing ().

In one preferred embodiment of the present invention olefin Homo - or copolymer obtained in the first stage of polymerization (A) has a porosity, expressed in percentage of voids, greater than 5%, preferably higher than 10%, more preferably higher than 15%.

Preferably, the polymers obtained in the first stage of polymerization (A), was characterized by macroporosity. Overall, more than 40% of the porosity of these polymers is due to pores with a diameter of more

The porosity, expressed in percentage of voids, and the distribution of the pore radius was determined by the mercury method, described below.

Upon receipt at the stage (C) kauchukopodobnoe copolymer, the porosity of the polymer obtained in the first stage of polymerization (A), gives the opportunity to work in the gas phase.

The amount of the polymer obtained in the first stage of polymerization (A), usually above 1000 g per 1 g of solid component, preferably above 2000 g to 1 g, more preferably above 3000 g per 1 g

The amount of polymer obtained at the stage of polymerization (A) is preferably, by weight, from 10 to 90% of the total amount of the polymer obtained in stage (a) and (C), and p the product of the reaction between:

i) a solid component comprising a compound of the transition metal MIselected from Ti and V and not containing links MI- printed on a substrate of magnesium halide in active form. This solid component may also contain an electron-donor compound (internal donor). Typically, this internal donor is used when the solid component used for obtaining catalysts for stereospecific polymerization of propylene, 1-butene and similar (-olefins, in which to prepare polymers with isotactic index greater than 90 high stereospecificity;

ii) alkylamine compound and optionally an electron-donor compound (external donor).

If stereoregular polymers receive the first stage of polymerization (I) (for example, polymers of propylene with a high isotactic index), the external donor is used to convey the catalyst necessary stereospecificity. However, if the internal donor is used, the diesters of the type described in the patent EP-A-361493, stereospecificity catalyst is high enough in and of itself, and the specified external donor is not required.

Halides m is widely known from the patent literature. Patent USP 4298718 and USP 4495338 was first described use of these compounds in catalysis by Ziegler-Natta. Of these patents, it is known that magnesium halides in the active form used as a substrate or apology components of catalysts for the polymerization of olefins, have x-ray spectra in which the most intense diffraction line appearing in the spectrum of active halide, decreases in intensity and is replaced by a line, the intensity of which is shifted towards smaller angles compared to the angles of the most intense line.

The connection specified transition metal MIpreferably chosen from the group consisting of: halides of titanium, halogen-alcoholate of titanium, VCl3, VCI4, VOCl3the halogen-alcoholate of vanadium.

Among the mentioned titanium compounds are preferred TiCl4TiCl3and halogen-alcoholate of the formula Ti(OR)mIXnin which RIrepresents a hydrocarbon radical with 1-12 carbon atoms or a group-CORIX represents a halogen, a (m+n) - valence titanium.

The specified catalytic component (i) preferably used in the form of spherical particles with cf is s, for example, in patents EP-A-395083, EP-A-553805, EP-A-553806 description concerning the method of obtaining and characteristics of these products, incorporated herein by reference.

Examples of internal donor compounds are ethers, esters, in particular esters of polycarboxylic acids, amines, ketones and 1,3-diesters of the type described in patents EP-A-361493, EP-A-361494, EP-A-362705 and EP-A-451645.

These alkylamines of compound (ii) is usually chosen from trialkylaluminium compounds, such as, for example, triethylamine, triisobutylaluminum, tri-n-butylamine, tri - n-hexylamine, tri-n-octylamine. You can also use a mixture of trialkylamine with halides alkylamine, hydrides alkylamine or single chlorides alkylamine, such as AlEt2Cl and Al2Et3Cl3.

External donors can be the same as internal donor, or may be different from them. When the internal donor is a polycarboxylic acid, such as a phthalate, the external donor is preferably selected from silicon compounds of the formula R1R2Si(OR)2where R1and R2represent alkyl, cycloalkyl or aryl radicals with 1-18 atom is l-tert-butyl-dimethoxysilane, dicyclopentadienyliron.

These compounds transition metal M used in the processing stage (b), selected from compounds of Ti, V, Zr and Hf containing at least one link with M-. Preferably, these compounds contain at least one ligand L having a mono - or polycyclic structure containing conjugated electrons, coordinated this metal M

The specified connection Ti, V, Zr or Hf, preferably selected from components having the following structure:

CpIMRa1Rb2Rc3(I)

CpICpIIMRa1Rb2(II)

(CpI-Ae-CpIIMRa1Rb2(III)

in which M represents Ti, V, Zr or Hf; CpIand CpIIidentical or different, represent cyclopentadienyls group or substituted cyclopentadienyls group; two or more substituents of the indicated cyclopentadienyls groups can form one or more cycles containing from 4 to 6 carbon atoms; R1, R2, R3the same or different, represent hydrogen atoms, halogen, alkyl or alkoxy group with 1-20 carbon atoms, aryl, alkylaryl and Rashi silicon atom; But alkanniny bridge or a bridge structure selected from:

< / BR>
< / BR>
< / BR>
= BR1, AlR1, -Ge-, -Sn-, -O-, -S-, =SO, =SO2=, =NR1, =PR1and =P(O)R1in which M1represents the Si, Ge or Sn; R1, R2identical or different, represent alkyl groups with 1-4 carbon atoms or aryl groups with 6-10 carbon atoms; a, b and C independently of one another are integers from 0 to 4; e is an integer from 1 to 6, and two or more radicals R1, R2and R3can form a cycle. When the Cp group substituted, the preferred Deputy is an alkyl group with 1-20 carbon atoms.

Typical compounds of formula (I) include: (Me5Cp)MMe3, (Me5Cp)M(OMe)3, (Me5Cp)MCl3, (Cp)MCl3, (Cp)MMe3, (MeCp)MMe3, (Me3Cp)MMe3, (Me4Cp)MCl3, (Ind)MBenz3, (H4Ind)MBenz3, (Cp)MBu3.

Typical compounds of formula (II) include: (Cp)2MMe2, (Cp)2MPh2, (Cp)2MEt2, (Cp)2MCl2, (Cp)2M(OMe)2, (Cp)2M(OMe)Cl, (MeCp)2MCl2, (Me5Cp)2MCl2, (Me5Cp)2MMe2, (Me5C(Me4Cp)2MCl2, (Me5Cp)2M(OMe)2, (Me5Cp)2M(OH)Cl, (Me5Cp)2M(OH)2, (Me5Cp)2M(C6H5)2, (Me5Cp)2M(CH3)Cl, (EtMe4Cp)2MCl2,

[(C6H5)Me4Cp]2MCl2, (Et5Cp)2MCl2, (Me5Cp)2M(C6H5)Cl, (Ind)2MCl2,

(Ind)2MMe2, (H4Ind)2MCl2, (H4Ind)2MMe2, {[Si(CH3)3]2Cp}2MCl2,

([Si(CH3)3]Cp}2MCl2, (Me4Cp)(Me5Cp)MCl2.

Typical compounds of formula (III) include:

C2H4(Ind)2MCl2C2H4(Ind)2MMe2C2H4(H4Ind)2MCl2C2H4(H4Ind)2MMe2, Me2Si(Me4Cp)2MCl2, Me2Si(Me4Cp)2MMe2, Me2SiCp2MCl2, Me2SiCp2MMe2, Me2Si(Me4Cp)2MMeOMe, Me2Si(Flu)2MCl2, Me2Si(2-Et-5-iPrCp)2MCl2, Me2Si(H4Ind)2MCl2, Me2Si(H4Flu)2MCl2, Me2SiCH2(Ind)2MCl2, Me2Si(2-MeH4Ind)2MCl2, Me2Si(2-MeInd)MCl2, Me2Si(2-Me-4,5 - benzhydryl)2MCl2, Me2Si(4,5-benzhydryl)2MCl2, Me2Si(2-EtInd)2MCl2,

Me2Si(2-iPrInd)2MCl2, Me2Si(2-tert-butyl-Ind)MCl2, Me2Si(3-tert-butyl-5-MeCp)2MCl2, Me2Si (3-tert-butyl-5-MeCp)2MMe2, Me2Si(2-MeInd)2MCl2C2H4(2-Me-4,5 - benzhydryl)2MCl2, Me2C(Flu)CpMCl2Ph2Si(Ind)2MCl2Ph(Me)Si(Ind)2MCl2C2H4(H4Ind)M(NMe2)OMe, isopropylidene-(3 - tert-butyl-Cp)(FLu)MCl2, Me2C(Me4Cp)(MeCp)MCl2, Me2Si(Ind)2MCl2, Me2Si(Ind)2MMe2,

Me2Si(Me4Cp)2MCI(OEt), C2H4(Ind)2M(NMe2)2C2H4(Me4Cp)2MCl2,

C2Me4(Ind)2MCl2, MeSi(3-MeInd)2MCl2C2H4(2-MeInd)2MCl2C2H4(3-MeInd)2MCl2C2H4(4,7-Me2Ind)2MCl2C2H4(5,6-Me2Ind)2MCl2C2H4(2,4,7-Me3Ind)2MCl2C2H3(3,4,7-Me3Ind)2MCl2C2H4(2-MeH4Ind)2MCl2C2H4(4,7-Me2H4In2,

Me2Si(5,6-Me2Ind)2MCl2, Me2Si(2,4,7-Me3H4Ind)2MCl2.

In the above simplified formula the symbols have the following meanings: Me = methyl, Et = ethyl, iPr = isopropyl, Bu = butyl, Ph = phenyl, Cp = cyclopentadienyl, Ind = indenyl, H4Ind = 4,5,6,7-tetrahydroindene, Flu = fluorenyl, Benz = benzyl, M = Ti, Zr or Hf, preferably Zr.

Join Me2Si(2-Mend)2ZrCl2and type Me2Si(2-MeH4lnd)ZrCI4and methods for their preparation are given in European patent application EP-A-485822 and 485820, the description of which is included as a reference.

Join Me2Si(3-tert-butyl-5-MeCp)2ZrCl2and type Me2Si(2-Me-4,4-benzhydryl)ZrCl2and the method of obtaining them is shown respectively in USP 5132262 and in European patent application EP-A-549900, the description of which is included as a reference.

The first stage of polymerization (A) can be carried out in liquid phase or in gas phase, in one or more reactors. Specified liquid phase may contain inert hydrocarbon solvent (suspension polymerization) or one or more olefins CH2=CHR (polymerization of the monomers in the liquid). Gas-phase polymerization can be conducted layers.

Stage of processing (C) is carried out mainly in two stages, the first (a) bringing into contact the polymer obtained at the polymerization stage (S), with a connection, which is able to deactivate the catalyst used at this stage (A), and at the second stage (b) bringing into contact the product obtained in step (a) with a solution of the transition metal M in hydrocarbon solvents (benzene, toluene, heptane, hexane, liquid propane, and the like).

Compounds that can be used at the stage of processing (a), you can choose from the group consisting of compounds of General formula Ry-xXH, where R is a hydrogen or hydrocarbon group with 1-10 carbon atoms, X represents O, N or S, and y is the valency of X.

Non-limiting examples of such compounds are alcohols, teopista, mono - and dialkylamino, NH3H2O and H2S. Preferred are those compounds in which X represents oxygen, and among them, particularly preferred is water.

Other examples of compounds that can be used at the stage of processing (a), CO, COS, CS2, CO2O2and acetylene or allene compounds.

Molar Otakon, to ensure significant deactivation of the catalyst stage (A). Preferably this ratio is higher than 50, more preferably above 150 and, in particular, more than 250.

The processing step (a), which specified decontamination connection lead in contact with the polymer obtained in stage (a) may be performed in different ways. One of them, this polymer is brought into contact with a hydrocarbon solvent containing this decontamination compound in solution, suspension or dispersion, for the period from 1 min to several hours. An example of dispersion deactivating compounds in the hydrocarbon solvent is wetted with hexane. At the end of the processing stage (a) the liquid is removed and the polymer is subjected to the processing (b).

The processing (b) is preferably carried out using the compound of the transition metal M in the solution of the hydrocarbon solvent containing dissolved alkylamino connection, such as triisobutylaluminum, triethylaluminum and/or alumoxane, for example, polymethylsiloxane (MAO), tetraisostearate or Tetra - (2,5-diethylhexyl)-alumoxane. The molar ratio alkylamino connection to the compound of the transition metal M is greater than 2, and prefocusing at the stage (a), the hydrocarbon solvent containing the dissolved transition metal compound and, optionally, alkylamino connection and/or alumoxane, usually carried out at temperatures from 0 to 100oC, preferably from 10 to 60oC, and removing the specified solvent at the end of this processing. Or the dry polymer obtained in stage (a) can be brought into contact with solutions of compounds of the transition metal M containing the minimum amount of solvent to save this compound in solution. Stage (C) is conveniently carried out in the gas phase in the reactor circulation, while the polymer obtained in the first polymerization is subjected to the circulation of a current of inert gas. Solutions deactivated compounds and the compounds of the transition metal M is served successively in the gas phase (e.g., spraying) in the reactor with circulation, and at the end of this processing gain slobodetski product. To the stage (b) this product is convenient to handle connections, is able to remove contaminants from the system, for example, alkylamines connections.

The amount of coupling of the transition metal M contained in the specified product obtained in stage (B) can menaitech of the target product at various stages. Usually this ranges from 110-7up to 510-3g metal M per 1 g of the product, preferably from 510-7up to 510-4and more preferably from 110-6110-4.

The second stage of polymerization (C) can be carried out in the liquid or in the gas phase in one or more reactors. This liquid phase may contain inert hydrocarbon solvent (suspension polymerization) or one or more olefins CH2=CHR (polymerization of the monomers in the liquid). Gas-phase polymerization can be carried out in fluidized bed reactors, or reactors with mechanical mixing layers. During this stage (S) in a polymerization reactor convenient to serve alkylamino a compound selected from trialkylaluminium compounds in which the alkyl groups have 1-12 carbon atoms, and linear or cyclic alumoxane compounds containing recurring Monomeric link -(R4)AlO-, where R4represents an alkyl group with 1-12 carbon atoms or cycloalkyl or aryl group with 6-10 carbon atoms, and these connections alumoxane contain from 1 to 50 repeating monomer unit. Typically, this alkylamino connection on the output connections.

The advantages of the process according to the present invention include both the quality of the final product and the versatility of the process. Indeed, stage (C) allows the use of different catalytic system for polymerization stages (a) and (C).

In particular, in the absence of the processing stage (s) would be necessary at the stage of (A) to receive so large a quantity of polymer that it has exhausted the activity of the catalyst at this stage. But it really entails getting too much of the product obtained at this stage. This should lead or to obtain the final product, which has dominated the part produced in stage (A) of this process, or to obtain the final product with balanced fractions obtained in stages (a) and (C), but with the wrong size of the polymer particles.

The process of the present invention can be used to produce a wide range of olefinic polymer compositions. In particular, this process is very suitable for producing high-impact polypropylene (heterophase copolymers of propylene). In this case, you can get elastomeric copolymers, motorcarrier with substantial elastomeric properties.

Indeed, the next aspect of the present invention is a process for heterophase propylene copolymers, characterized in that it includes:

(A) the first stage of polymerization, which will polimerizuet propylene and possibly ethylene and/or one or more olefins CH2=CHRIIin which RIIrepresents a hydrocarbon radical with 2 to 10 carbon atoms in one or more reactors in the presence of a catalyst containing reaction product between alkylamine compound, optionally an electron-donor compound (external donor) and a solid component comprising at least one compound of the transition metal MIselected from Ti and V, not containing links M-, and magnesium halide in active form and, optionally, an electron-donor compound (internal donor). While having olefinic polymer, the porosity of which, expressed as percentage of voids, is more than 10%, the content of monomer units derived from ethylene and/or CH2=CHRIIthe olefin is by weight less than 20%, the content of monomer units derived from propylene by weight more than 80%, and the insolubility in xylene - more than 60%;

(C) static in contact with the connection, able to deactivate the catalyst, is present at this stage (A); and

b) bring into contact with the compound of the transition metal M selected from Ti, Zr, V or Hf containing at least one communication M and, optionally, with alkylamines connection.

(C) second stage of polymerization in which one or more of the olefins CH2= CHR, where R represents hydrogen, alkyl, cycloalkyl or aryl radical with 1-10 carbon atoms, are polymerized in one or more reactors, in the presence of the product obtained at this stage of processing (In). You get a substantially amorphous olefin (co)polymer, its amount is from 20 to 80% by weight of the total polymer obtained in stage (a) and (C).

The polymer obtained in the first stage of polymerization (A) is preferably a propylene homopolymer with a high rate of isotacticity or crystalline copolymer of propylene with a weight content of monomer units derived from ethylene and/or CH2=CHRIIolefins, less than 10%.

Non-limiting examples of substantially amorphous olefin (co) polymers which can be obtained from the propylene with fewer diene, with weight content of monomer units derived from ethylene, from ~30 to 70%; elastomeric copolymers of ethylene and butene and elastomeric ternary copolymers of ethylene, butene and propylene with a weight with the content of monomer units derived from ethylene, from ~ 30 to 70%; atactic polypropylene with high molecular weight (>1). Examples of these copolymers are described in European patent application EP-A-586658, EP-A-604917 and in the patent application Italy M-A, MI-A, MI-A, MI-A and M-A, referenced in part, related to the characteristics of these products and catalysts used to produce it.

Stage of polymerization (A) is conveniently carried out in liquid propylene, one or more reactors, circulation, or in the gas phase, using a fluidized bed reactors or with mechanical mixing layers. Preferred is a gas-phase technology fluidized bed.

Stage polymerization (C) preferably takes place in one or more reactors in a gas phase fluidized bed. You can also use other technologies (for example, suspension polymerization or polymerization in the gas phase when mechanically mixed layer).

Preferred Pori who leaves more than 15%, and more preferably above 20%. The distribution of the pores is such that more than 40% of the porosity is due to pores with diameter more Preferably, when the high porosity of more than 90% porosity was due to pores with a diameter of more

The amount of polymer obtained at the stage of polymerization (C) is preferably from 25 to 75% by weight of the total polymer obtained in stage (a) and (C), more preferably from 35 to 65%.

It is preferable to carry out the process continuously, conducting both phase polymerization (a) and (C) in gas-phase fluidized bed reactors and the processing phase (C) in the gas-phase reactor with circulation. Polymerization stage (A) is preferably preceded by a stage of terpolymerization in which propylene or mixtures thereof with ethylene and/or CH2=CHRIIthe olefins will polimerizuet in the presence of the catalyst described in paragraph (A), in the amount of from 5 to 500 g per 1 g of catalyst.

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

Porosity and surface area determined by nitrogen was determined by the method of C. E. T. (equipment used: SORPTOMATIC 1800 from Carlo Erba).

The particle size of the catalysis is Veta equipment Malvern Instr. 2600". The average size amounted to R50.

Index melting E (MIE) was determined according to ASTM-D 1238, a method that is

Index melting F (MIF) was determined according to ASTM-D 1238, method F.

Attitude index (F/E) is the ratio between the index of fusion F and the index of fusion that is

Index melting L (MIL) was determined according to ASTM-D 1238 method L.

Fluidity is the time required for the flow to 100 g of the polymer through the funnel, the outlet of which has a diameter of 1.25 cm and walls of which form an angle of 20owith the vertical.

Density; DIN 53194.

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

Fraction soluble in xylene, measured by dissolving the polymer in hot xylene and the determination of insoluble residue after cooling to 25oC.

The content of the co monomer is the percentage of co monomer by weight, determined by infrared spectroscopy.

The effective density: ASTM-D 792.

Porosity: the porosity, expressed as percentage of voids is determined by the absorption of mercury under pressure. The amount of absorbed mercury corresponds to the pore volume. To make this determination, use calibrated dilatometer amount of sample (~0.5 g) is placed in the dilatometer. Then this device is placed in a high vacuum of < 0.1 mm Hg) and within 10 min survive in these conditions. Then the dilatometer attached to the mercury reservoir and allowed to slow the flow of mercury in it up until the mercury reaches the mark made on the dilatometer at a height of 10 cm, the Valve connecting the dilatometer with the pump cover and the pump device nitrogen (2.5 kg/cm2). Under the influence of high pressure mercury penetrates into the pores and its level is reduced in accordance with the porosity of the material. Measuring the level at which mercury has been established, calculate the pore volume, based on the equation V =2N, where R is the radius of the dilatometer, and H is the difference in cm between the initial and final levels of copper in the dilatometer. Weighing the dilatometer, the dilatometer + mercury, dilatometer + mercury + sample, one can calculate the apparent volume of the sample V1before the penetration of mercury into its pores. This sample volume defined by the equation:

V1=[P1-(P2-P)]/D

where P is the weight of sample in g, P1- the weight of the dilatometer + mercury (g), P2- the weight of the dilatometer + mercury + sample (g), D is the density of mercury (at 25oC it is 13.546 g/cm3). The percentage of pores is given by the ratio X = (100V)/V1.


Stage (A): Obtaining polypropylene homopolymer

In a 50 ml glass flask 0.0161 g of solid catalytic component obtained according to example 3 of European patent application EP-A-395083, pre-contacted with 0.7999 g triethylaluminum (TEAL) and 0.31 g cyclohexylmethyl-dimethoxysilane (CMMS) in 8 ml anhydrous hexane. The resulting mixture was introduced into a steel autoclave with a capacity of 4.25 l pre-cleaned by washing first for 1 h at 80oC hexane, and then for 1 h at 80oC gaseous propylene. Next introduced 1752 g of liquid propylene with 982 ml of hydrogen at 30oC. the Temperature was raised to 70oC for 180 min were in the polymerization. This was 248 g of propylene with the following characteristics: IV= 1.55 DL/g, insoluble in xylene substance = 96% by weight.

Stage (s): Copolymerization of ethylene and propylene

After removal of propylene in the same reactor was loaded with 500 g of liquid propane at a temperature of 50oC and a pressure of 19.5 bar. Then introduced 7 mmol M-MAO dissolved in ISOPAR C, and the resulting mixture is left in contact with the polymer for 10 min at 50oC. the Propane was removed by evaporation when 50oC, and to remove any residual propane spent several who bavili 19.3 g of ethylene and 41.6 g of propylene. Introducing a mixture of two monomers, containing 60% by weight of ethylene, carried out the polymerization. The copolymerization was carried out at 50oC and 9 bar for 120 minutes Was obtained 276 g of the copolymer with the characteristics given in table. 1.

EXAMPLE 2 (comparative)

Stage (A): Obtaining polypropylene homopolymer

The catalyst and the propylene homopolymer was obtained as described in stage (A) of example 1. The polymerization was performed using 0.0132 g of solid catalytic component. Received 209 g homopolymer with the following characteristics:

IV = 1.57 DL/g; the insolubility in xylene = 96.1% by weight.

Stage (): Handle (b) with EBTHI-ZrCI2< / BR>
After removal of propylene in the same reactor was loaded with 500 g of liquid propane at 50oC and a pressure of 19.5 bar. Then introduced 0.005 g EBTHI-ZrCl2pre-exposed in ISOPAR 10 min at 25oC 11.7 mmol M-MAO. The resulting mixture is left in contact with the polymer for 10 min at 50oC. the Propane was removed by evaporation when 50oC, and to remove any residual propane spent several washings with gaseous propylene.

Stage (s): copolymerization of ethylene and propylene

Followed the procedure described in stage (C) the use is recommended in table 1.

EXAMPLE 3

Stage (A): Obtaining polypropylene homopolymer

The catalyst and the propylene homopolymer was obtained as described in stage (A) of example 1. The polymerization was performed using 0.0146 g of solid catalytic component. Received 186 g homopolymer with the following characteristics: IV = 1.57 DL/g; the insolubility in xylene = 96.1% by weight.

Stage (): Processing (a) water and process (b) using EBTHI-ZrCl2< / BR>
After degassing of the propylene in the same reactor downloaded 1000 ml of hexane, moist 0.0513 g of water. He was left in contact with the polymer for 30 min at 50oC in nitrogen atmosphere. The liquid was removed by siteniravam and spent several cyclic washes at room temperature using vacuum and nitrogen. In the same reactor was loaded with 500 g of liquid propane at 50oC and a pressure of 19.5 bar. Then introduced 0.005 g EBT-HI-ZrCI2pre-exposed in ISOPAR 10 min at 25oC 11.7 mmol M-MAO. The resulting mixture is left in contact with the polymer for 10 min at 50oC. the Propane was removed by evaporation when 50oC, and to remove residues spent several washings with gaseous propylene.

Stage (s): copolymerization of ethylene and propylene

Followed the 56 g of copolymer with characteristics listed in table 1.

EXAMPLE 4 (comparative)

Stage (A): Obtaining polypropylene homopolymer

In a 50 ml glass flask 0.0187 g of solid catalytic component obtained according to example 3 of European patent application EP-A-395083, previously brought into contact with 1.48 g of triisobutylaluminum (TIBAL) and 0.0706 g cyclohexyltrichlorosilane (CMMS) in 8 ml anhydrous hexane. The resulting mixture was placed in a steel autoclave with a capacity of 4.25 l, which was pre-cleaned by a sufficient number of washing, first with hexane at 80oC for 1 h, and then with gaseous propylene at 80oC for 1 h and Then at 30oC introduced 1286 g of liquid propylene. The temperature was raised to 70oC, and polymerization was carried out for 120 minutes resulted In 32 g of homopolymer with the following characteristics: IV = 5.68 DL/g, the insolubility in xylene = 89.7% by weight.

Stage (C); the copolymerization of ethylene and propylene

After degassing of the propylene in the same reactor was loaded with 500 g of liquid propane at 50oC and a pressure of 19.5 bar. Then introduced 9.38 mmol TIBAO, dissolved in cyclohexane, and the resulting mixture is left in contact with the polymer for 10 min at 50oC. Propane deleted isparana 50oC. To the resulting product in the same reactor at 50oC added 33.8 g of ethylene and 72.9 g of propylene. The resulting copolymer composition was kept constant by feeding a mixture of these monomers, containing by weight 60% ethylene. The copolymerization was carried out for 245 min at 50oC and 15 bar. Received 315 g of a copolymer having the characteristics listed in table 2.

EXAMPLE 5 (comparative)

Stage (A): Obtaining polypropylene homopolymer

The catalyst and the propylene homopolymer was obtained as described in stage (A) of example 4. The polymerization was performed using 0.02 g of solid catalytic component. Received 69 g homopolymer with the following characteristics: IV = 4.69 DL/g; the insolubility in xylene = 82% by weight.

Stage (): Handle (b) with EBTHI-ZrCL2< / BR>
After degassing of the propylene in the same reactor was loaded with 500 ml of liquid propane at 50oC and a pressure of 19.5 bar. Then introduced 0.004 g EBTHI-ZrCl2pre-exposed in cyclohexane for 10 min at 25oC 9.38 mmol TIBAO. The resulting mixture is left in contact with the polymer for 10 min at 50oC. the Propane was removed by evaporation when 50oC, and to remove residues spent bore the Followed methodology, described in stage (C) of example 1, a copolymerization was carried out for 54 minutes When this was received 353 g of the copolymer with the characteristics listed in table 2.

EXAMPLE 6

Stage (A): Obtaining polypropylene homopolymer

The catalyst and the propylene homopolymer was obtained as described in stage (A) of example 4. The polymerization was performed using 0.0414 g of solid catalytic component. Got 170 g homopolymer with the following characteristics: IV = 4.4 DL/g; the insolubility in xylene = 85.3% by weight.

Stage (): Processing (a) water and process (b) using EBTHI-ZrCl2< / BR>
After degassing of the propylene in the same reactor downloaded 1000 ml of hexane, moist 0.068 g of water. He was left in contact with the polymer for 30 min at 50oC in nitrogen atmosphere. The liquid was removed by siteniravam and spent several cyclic washes at room temperature using vacuum and nitrogen. In the same reactor was loaded 1.48 g of TIBAL dissolved in 500 g of liquid propane at 50oC and a pressure of 19.5 bar. The polymer is left in contact with this mixture for 20 min at 50oC. Then introduced 0.020 g EBTHI-ZrCl2pre-exposed in cyclohexane with 46.9 mmol TIBAO for 10 min at 25ooC, and to remove residues spent several washings with gaseous propylene.

Stage (s): copolymerization of ethylene and propylene

Followed the procedure described in stage (C) of example 1, a copolymerization was carried out for 81 minutes, this was 260 g of the copolymer with the characteristics specified in table 2.8

1. Multi-stage method for the polymerization of one or more olefins of the formula

CH2=CHR,

where R represents hydrogen or alkyl, cycloalkyl or aryl group with 1-10 carbon atoms,

characterized in that it includes: (a) the first stage of polymerization in which to obtain the olefin Homo - or copolymer will polimerizuet one or more of these olefins in one or more reactors in the presence of a catalyst containing reaction product between alkylamine compound and a solid component comprising a compound of the transition metal MIselected from the group consisting of titanium and vanadium, which do not contain links MI- and a magnesium halide in active form; (C) the machining stage, during which the product obtained in the first stage of polymerization (A) by any method (a) is brought into contact with the compound capable of agodnego metal M, selected from the group consisting of titanium, zirconium, vanadium, or hafnium containing at least one link with M - s, optional, alkylamines connection; (C) the second stage of polymerization in which one or more of these olefins will polimerizuet in one or more reactors, in the presence of the product obtained at this stage of processing ().

2. The method according to p. 1, characterized in that the Homo - or copolymer obtained in stage (A) has a porosity, expressed in percentage of voids, higher than 5%.

3. The method according to p. 2, characterized in that the Homo - or copolymer obtained in stage (A) has a porosity, expressed in percentage of voids, higher than 10%.

4. The method according to p. 1, characterized in that the magnesium halide in active form using magnesium chloride, and the compound of the transition metal MIselected from the group consisting of halides of titanium, galogenangidridy titanium, VCl3, VCl4, VOCl3galogenangidridy vanadium.

5. The method according to p. 4, characterized in that the connection specified titanium is chosen from the group consisting of TiCl4, TiCl3and galogenangidridy formula

Ti(OR1)Rupp COR1;

X represents a halogen;

(m+n)-valence titanium.

6. The method according to p. 1, characterized in that the solid component used in the first stage of polymerization (A), has the form of spheroidal particles with an average diameter of 10 to 150 μm.

7. The method according to p. 1, characterized in that the compound of the transition metal M contains at least one ligand L coordinated this metal, and the specified ligand is mono - or polycyclic structure containing conjugated electrons.

8. The method according to p. 7, characterized in that the compound of the transition metal M selected from

Cf1MR1aR2bR3c (1)

Cp1Cp11MR1aR2b (2)

(Cp1-Ae-Cp11MR1aR2b (3)

in which M represents Ti, V, Zr or Hf;

Cp1or Cp11identical or different, represent cyclopentadienyls group or substituted cyclopentadienyls group; two or more substituents of the indicated cyclopentadienyls groups can form one or more cycles containing from 4 to 6 carbon atoms;

R1, R2, R3identical or different, represent hydrogen atoms, Gal is alloctype with 1-20 carbon atoms, allyl group, Deputy containing a silicon atom;

But alkanniny bridge or a bridge structure selected from:

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
=BR1, =AlR1, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR1, =PR1.

9. The method according to p. 8, characterized in that the compound of the transition metal M selected from compounds having the following structure: (Me5Cp)Miu3, (Me5Cp)M(OMe)3, (Me5Cp)MCl3, (Cp)MCl3, (Cp)Miu3, (MeCp)Miu3, (Me3Cp)Miu3, (Me4Cp)MCl3, (Ind)MBenz3, (H4Ind)MBenz3, (Cp)MBu3where Me is methyl, Cf - disclosed previously, Benz - benzyl, Ind - indenyl, Bu is butyl.

10. The method according to p. 8, characterized in that the compound of the transition metal M is chosen from compounds

(Cp)2MMe2, (Cp)2MPh2, (Cp)2Met2, (Cp)2MCl2, (Cp)2M(OMe)2,

(Cp)2M(OMe)Cl, (MeCp)2MCl2, (Me5Cp)2MCl2, (Me5Cp)2MMe2,

(Me5Cp)2MMeCl, (Cp)(Me5Cp)MCl2, (l-MeFlu)2MCl2, (BuCP)2MCl2,

(Me3Cp)2MCl2), (Me4Cp)2MCl2, (Me5Cp)2M(OMe)2, (Me5Cp)2M(OH)Cl, (MeCp)2MCl2, [(C6H5)Me4Cp]2MCl2, (Et5Cp)2MCl2, (Me5Cp)2M(C6H5)Cl, (Ind)2MCl2, (Ind)2MMe2, (H4Ind)2MCl2, (H4Ind)2MMe2, {[Si(CH3)3]2Cp}2,

{[Si(CH3)3]Cp}2MCl2, (Me4Cp)(Me5Ch)MCl2.

11. The method according to p. 8, characterized in that the compound of the transition metal M choose Saedinenie

C2H4(Ind)2MCl2C2H4(Ind)2MMe2C2H4(H4Ind)2MCl2C2H4(H4Ind)2MMe2, Me2Si(Me4Cp)2MCl2, Me2Si(Me4Cp)2MMe2, Me2SiCp2MCl2, Me2SiCp2MMe2, Me2Si(Me4Cp)2MMeOMe, Me2Si(Flu)2MCl2, Me2Si(2-Et-5-iPrCp)2MCl2,

Me2Si(H4Ind)2MCl2, Me2Si(H4Flu)2MCl2, Me2SiCH2(Ind)2MCl2,

Me2Si (2-MeH4Ind)2MCl2, Me2Si (2-Me-Ind)2MCl2, Me2Si(2-Et-5-iPrCp)2MCl2, Me2Si(2-Me-5-EtCp)2MCl2, Me2Si(2-Me-5-MeCp)2MCl2,

Me2Si(2-Me-4B>2
, Me2Si(2-iPrInd)2MCl2, Me2Si(2-tert-butyl-Ind)MCl2, Me2Si(3-tert-butyl-5-MeCp)2MCl2, Me2Si(3-tert-butyl-5-MeCp)2MMe2,

Me2Si(2-MeInd)2MCl2C2H4(2-Me-4,5-benzhydryl)2MCl2,

Me2C(Flu)CpMCl2Ph2Si(Ind)2MCl2Ph(Me) Si(Ind)2MCl2,

C2H4(H4Ind)M(NMe2)OMe, isopropylidene-(3-tert-butyl-CP)(Flu)MCl2,

Me2C(Me4Cp)(MeCp)MCl2, Me2Si(Ind)2MCl2, Me2Si(Ind)2MMe2,

Me2Si(Me4Cp)2MCl (Oet), C2H4(Ind)2M(NMe2)2C2H4(Me4Cp)2MCl2C2Me4(Ind)2MCl2, MeSi(3-MeInd)2MCl2C2H4(2-MeInd)MCl2,

C2H4(3-MeInd)2MCl2C2H4(4,7-Me2Ind)2MCl2C2H4(5,6-Me2Ind)2MCl2C2H4(2,4,7-Me3Ind)2MCl2C2H4(3,4,7-Me3Ind)2MCl2,

C2H4(2-MeH4Ind)2MCl2C2H4(4,7-Me2H4Ind)MCl2,

C2H4(2,4,7-Me3H4Ind)2MCl2, Me2Si(4,7-Me2Ind)2MCl2
/P>12. The method according to p. 1, characterized in that the first stage polymerization using a catalyst containing reaction product between alkylamine compound, an electron-donor compound, which represents an external donor, and a solid component containing at least one compound of the transition metal MIselected from the group containing titanium or vanadium, and do not contain links MI- and a magnesium halide in active form and an electron-donor compound, representing the internal donor.

13. The method according to p. 12, characterized in that the electron-donor compound (external donor) selected from silicon compounds of the formula

R1R2Si(OR)2,

where R1and R2may be the same or different and represent alkyl, cycloalkyl or aryl group with 1-18 carbon atoms;

R represents an alkyl radical with 1-4 carbon atoms.

14. The method according to p. 1, characterized in that the specified connection, deactivating the catalyst used in stage (B) polymerization is chosen from the group consisting of CO, COS, CS2, CO2O2, acetylene compounds, allene compounds and compounds and carbon;

X represents O, N or S;

y is the valency of X.

15. The method according to p. 1, characterized in that the compound capable of deactivating the catalyst used in the first stage polymerization, use water.

16. The method according to p. 1, characterized in that in stage (B) the product obtained in the first stage of polymerization (A) is brought into contact with a solution, suspension or dispersion mixture decontamination compounds in aliphatic hydrocarbons containing such quantity of deactivating connections that the molar ratio of the compounds to MIexceed 50, and the specified product is subsequently subjected to treatment with a solution containing a specified compound of the transition metal M and alkylamino a compound selected from trialkyl aluminum, in which the alkyl groups contain 1-12 carbon atoms, and linear or cyclic compounds alumoxane with repeating Monomeric units -(R4)AlO-, where R4represents an alkyl group with 1-12 carbon atoms or cycloalkyl or aryl group with 6-10 carbon atoms, and these connections alumoxane contain 1-50 recurring Monomeric units.

17. Method m reactions, obtained at the stage of processing (C), and at the same time or separately alkylamines a compound selected from trialkyl aluminum, in which the alkyl groups contain 1-12 carbon atoms, and optionally linear or cyclic compounds alumoxane containing recurring Monomeric link -(R4)AlO-, where R4represents an alkyl group with 1-12 carbon atoms or cycloalkyl or aryl group with 6-10 carbon atoms, and these connections alumoxane contain 1-50 recurring Monomeric units.

18. The method according to p. 1, characterized in that the polymerization stage (A) is carried out in the liquid phase containing hydrocarbon solvent or one or more olefins CH2=CHR, and curing stage (C) conduct at least one fluidized bed reactor or mechanically mixed layer.

19. The method according to p. 1, characterized in that at both stages (a) and (C) the polymerization is carried out in gas-phase reactors with a fluidized bed or a mechanically mixed layer.

20. The method according to p. 1, characterized in that the machining stage (C) is carried out in gas-phase reactor with circulation.

21. The method according to p. 1, characterized in that the number on the s (a) and (C).

22. The method according to p. 1, characterized in that the polymer obtained in stage (A) comprises by weight from 20 to 80% of the total amount of the polymer obtained in stage (a) and (C).

23. Multistage method for heterophase propylene copolymers, characterized in that it includes a first stage of polymerization in which one or more of the reactors will polimerizuet propylene, and ethylene and/or one or more olefins CH2=CHRIIwhere RIIrepresents a hydrocarbon radical with 2 to 10 carbon atoms in the presence of a catalyst containing reaction product between alkylamine compound, optionally an electron-donor compound used as external donor, and a solid component comprising a compound of the transition metal MIselected from the group consisting of titanium and vanadium, which do not contain links MI- and a magnesium halide in active form, and, optionally, an electron-donor compound used as an internal donor, to obtain the olefin polymer, the porosity of which, expressed as percentage of voids, greater than 10%, the content of monomer units derived ethylene and/or olefin CH2= C is at over 80% and the insolubility in xylene of more than 60%; (C) the stage of processing at which the specified product obtained in the first stage (A), in any manner (a) bring into contact with a compound capable of deactivating the catalyst, is present at this stage (A) and (b) is brought into contact with the compound of the transition metal M selected from the group consisting of titanium, zirconium, vanadium, or hafnium containing at least one link with M - and possibly alkylamines connection with) the second stage of polymerization, which will polimerizuet one or more olefins CH2= CHR, where R represents hydrogen, alkyl, cycloalkyl or aryl radical with 1-10 carbon atoms, carried out in one or more reactors, in the presence of the polymerization product obtained in the processing phase, (B) receive substantially amorphous olefin copolymer, the amount of which is, by weight, from 20 to 80% of the total amount of the polymer obtained in stage (a) and (C).

24. Olefin Homo - and copolymers, characterized in that they are obtained by the process described in paragraph 1 or 23.

 

Same patents:

- olefins and method of reception" target="_blank">

The invention relates to precatalytic compositions suitable for Homo - and copolymerization of olefins and to a method for producing such composition precatalytic

The invention relates to precatalytic component of the catalytic composition of the Ziegler-Natta, suitable for the production of polymers of ethylene

The invention relates to a ball of solid catalytic components for the polymerization of olefins containing compound of titanium deposited on a magnesium halide containing more than one relationship Ti-halogen and, optionally, containing groups other than halogen, in the amount of less than 0.5 mol per 1 mol Ti

The invention relates to a method for producing olefinic polymers (this is the name used to refer to both homopolymers and copolymers of olefins by polymerization (the term used to refer to as homopolymerization and copolymerization) of olefins

The invention relates to copolymers of ethylene,-olefin containing from 3 to 18 carbon atoms, and unpaired-omega diene having at least 7 carbon atoms and having two easily curable double bonds, the number of non-conjugate diene is 0.005 to 0.7 mol

The invention relates to catalytic systems, methods for their preparation and their use in polymerization of olefins

-olefin (options)" target="_blank">

The invention relates to catalysts used for Homo - and copolymerization of ethylene and other olefin hydrocarbons

The invention relates to thermoplastic polyolefins, with the ability to recycle and to methods for their preparation

The invention relates to the synthesis of low molecular weight branched polyethylene in the presence of efficient homogeneous catalytic systems based on metallocene or pseudometallic complexes IVC group, alyuminiiorganicheskikh compounds and perftoralkil borates

The invention relates to new Homo - and copolymers of ethylene having a degree of swelling at least 1,4, resistance to cracking under load at least 55 h and the flow index of at least 0.2 g/10 min
Up!