Bimetallic catalyst for the (co)polymerization of alpha-olefins

 

Bimetallic catalyst for the (co)polymerization-olefins, including socialization consisting of a hydride or ORGANOMETALLIC compound of item 1, 2 or 13 group of the Periodic table and a solid component comprising at least 95 wt.% titanium, magnesium, hafnium, aluminum, chlorine and carboxylate groups R-COO in the following molar ratios: M/Ti=0,1-10,0; Mg/Ti=1,0-20,0; Al/Ti=0,01-6,0; Cl/Ti=2,0-70,0; R-COO/Ti=0,1-10,0, where R is aliphatic, cycloaliphatic or aromatic hydrocarbon containing from 1 to 30 carbon atoms, in which at least 80% of the titanium is in the oxidation state +3, and at least 1% of the specified titanium in oxidation state +3 has a tetrahedral coordination configuration. The specified catalyst allows to obtain olefin polymers, in particular polyethylene, high molecular weight in processes with high productivity by polymerization in solution at temperatures higher than 200°C. 4 C. and 26 C.p. f-crystals, 1 tab., 2 Il.

The present invention relates to a bimetallic catalyst, its method of preparation and to its use in processes catalyst for the (co)polymerization-olefins of the type of the catalyst of the Ziegler-Natta comprising a solid component containing titanium, and socialization consisting of a hydride or ORGANOMETALLIC compound of item 1, 2 or 13 group of the Periodic table (in the form approved by IUPAC and published by CRC Press Inc.” in 1989, links to which are listed hereinafter). This catalyst can be obtained using the original method proposed by the applicant.

It is known that ethylene, or-olefins in General, can be subjected to polymerization by a process of low, medium or high pressure on the catalyst type catalysts, Ziegler-Natta, with the formation of essentially linear polymers with high molecular weight. These catalysts usually consist of compounds of elements of 4-6 groups of the Periodic table in contact with the ORGANOMETALLIC compound or hydride of items 1, 2 or 13 group of the Periodic table.

The solid components of the catalyst of the Ziegler-Natta containing a transition metal (usually titanium), ferrous metal (usually magnesium), halogen (usually chlorine), and possibly electron donor, known in the art. These solid components used in conjunction with metalloprotease, carried out at low temperature and pressure. For example, in patent US 3642746 described solid catalyst component obtained by contact of the compound of the transition metal halide of the divalent metal processed by the electron donor. In accordance with the patent US 4421674 a solid component of catalyst is obtained by contact of the compound of the transition metal with the product of the spray drying of a solution of magnesium chloride in ethanol.

In accordance with UK patent 1401708 a solid component of catalyst is obtained by interaction of the halide of magnesium, dehalogenating compounds of the transition metal and aluminum halide. Patents US 3901863 and US 4292200 describe the solid component of catalyst obtained by contacting each other dehalogenating compounds of magnesium, dehalogenating compounds of the transition metal halide of aluminum.

In the patent US 4843049 and European patent application EP-A 243327 described solid catalyst component which contains titanium, magnesium, aluminum, chlorine and CNS group and has a high activity in the processes (co)polymerization of ethylene is carried out at low pressure and temperature of the suspension in a manner or at high pressure and temperature, Alnoy drying ethanol solution of magnesium chloride to obtain active media which is sequentially introduced into the reaction tetraethoxide titanium or titanium tetrachloride and alkylamidoamines respectively.

All these catalysts, although relatively active in the specified process, however, is not entirely satisfactory in regard to the properties of the obtained polymer or copolymer, among which the most noteworthy is the average molecular mass, particularly for polyolefins obtained in high-temperature processes, which are still unsuitable for certain industrial applications. In addition, there are still opportunities for further increasing the activity of the above catalyst.

Attempts were made to modify the properties of polymers or copolymers of olefins using catalysts based on a mixture of transition metals. For example, in European patent EP-A 177189 and European patent EP-A 146507 described the preparation and use of catalysts of the type of catalyst, Ziegler-Natta, including titanium and hafnium, to obtain polyethylene with advanced (bimodal) molecular weight distribution. The method of obtaining these catalysts includes the introduction of titanium and hafnium in two different stages.

In the European patentit solid components of catalyst, with the generally higher activity in the processes (co)polymerization of ethylene and-olefins, in the process carried out at low pressure and temperature, at high pressure and temperature and in solution, and in the nature of the thus obtained polymers in comparison with the known in the art catalysts. The catalysts containing metal carboxylate, carried out through a complex process, which involves mixing the previously prepared solutions of carboxylates of magnesium and transition metal in an organic hydrocarbon solvent. The disadvantage of this method, however, is that it does not allow complete freedom in the choice of the atomic ratios between the metals in the catalyst because of their different solubility in hydrocarbon solvents.

Currently, the applicant has found that polymers and copolymers-olefins, with high molecular weight can be obtained, surprisingly, in processes with high productivity in high-temperature conditions using a special bimetallic catalyst type catalyst of the Ziegler-Natta, newline.

In line with this, firstly, the present invention relates to a solid component of catalyst for the (co)polymerization-olefins, comprising at least 95 wt.%, preferably 98-100 wt.%, titanium, magnesium, at least one metal selected from hafnium, zirconium, aluminum, chlorine, and R-COO of carboxylate, in the following molar proportions:

M/Ti=0,1-10,0; MD/Ti=1,0-20,0; Al/Ti=0,01-6,0;

Cl/Ti=2,0-70,0; R-COO/Ti=0,1-10,0,

where R is aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing from 1 to 30 carbon atoms, and M is a metal selected from hafnium and zirconium or one of their mixtures, and is preferably hafnium, which is characterized by the fact that at least 80%, preferably at least 90% of the titanium is in the oxidation state +3, and, in addition, at least 1%, preferably from 2 to 10%, of the specified titanium in oxidation state +3 has a tetrahedral coordination configuration.

The number of carbon atoms of the radical R of the specified carboxylate is not Particularly critical, but preferably it is in the range from 6 to 15.

The term “(co)polymerization in the form in which it is used in this description is the-olefin, such as ethylene - with the formation of crystalline high-density polyethylene or propylene - with the formation of polypropylene, as well as copolymerization-olefin with at least one different unsaturated compound capable of copolymerisate with him (obviously representing different-olefin) such as the copolymerization of ethylene with ethylidenenorbornene education capable of cross-linking of polyethylene or copolymerization of ethylene with 1-butene with the formation of linear low density polyethylene.

For simplicity, the term “mole” and “molar ratio” used in the present description and claims and with respect to compounds consisting of molecules, and also in relation to atoms and ions, avoiding relative to the last term of the gram-atom or atomic ratio, even given their greater scientific validity.

In accordance with another aspect, the present invention relates to a process of manufacturing the above solid catalyst component, comprising the following successive stages:

(i) preparation of a mixture of at least one connection m consisting of inert organic liquid, in which at least one of these components insoluble;

(ii) preparation of essentially transparent solution by adding to the said mixture of stage (i) a sufficient number of carboxylic acid having the formula R-COOH (I), where R is aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing from 1 to 30 carbon atoms, and maintaining the mixture at suitable conditions of temperature and pressure to essentially complete dissolution of all insoluble compounds;

(iii) adding to the solution obtained in stage (ii), and the interaction with them alkylhalogenide, which may be represented by the following General formula (II):

where R’ is a linear or branched alkyl radical containing from 1 to 20 carbon atoms, and “n” is a decimal number whose values are in the range from 0.5 to 2.5, preferably from 0.9 to 2.1;

in a quantity at least sufficient to at least 70%, preferably 80% of the titanium present in the solution in this stage (ii), precipitate in the form of a solid connection,

(iv) separating the solids deposited on the stage (iii) of the remaining W is de it is used in the present description and the claims, relative to the mixture of a solid in a liquid, means that more than 90% of the specified solid remains undissolved in the specified fluid.

The liquid used for preparing the mixture of stage (i) of the process may be any organic liquid, inert (preaction-able) in relation to the other components of the mixture. In particular, this inert solvent should be at least aprotic, i.e. do not have reactive acidic protons, such as protons alcohol, amine or acid groups. Able to coordinate organic liquid, i.e., capable of forming adducts with metal ions, which form the above-mentioned solid catalyst component, are also considered to be reactive and therefore inadmissible in accordance with the present invention. Non-polar or slightly polar liquid and, in particular, aliphatic, cycloaliphatic or aromatic hydrocarbons that are liquid under the conditions of this production, such as, for example, hexane, heptane, octane, Nanan, decane, undecane, dodecane, cyclopentane, cyclohexane, benzene, toluene, xylenes and mesitylene, predatelistvo of the present invention are the following, in which:

the radical R is a linear alkyl containing at least 4 carbon atoms; for example, group n-butyrate, n-octoate, n-decanoate, n-undecanoate and n-dodecanoate;

the radical R is a branched alkyl branch on the secondary carbon atom located in the-position relative to the carbon atom of the carboxylic group:

where the sum of carbon atoms in R1and R2equal to at least 2; for example, groups of isobutyrate, 2-methylbutyrate and 2-ethylhexanoate;

the radical R is a branched alkyl with two branches at the Quaternary carbon atom located in the-position relative to the carbon atom of the carboxylic group:

where the sum of carbon atoms in R3, R4and R5equal to at least 3;

for example, the group of 2,2-dimethylpropanoate and versatate;

the radical R is alkyl with a branch to the secondary carbon atom located in the-position relative to the carbon atom of the carboxylic group:

where the sum of carbon atoms in R6and R7equal at mercinary:

R8-(CH2)s-COO

where R8represents cycloalkyl or aryl residue, monocyclic or multiple condensed or unfused cycles, a “s” is an integer varying from 0 to 10; for example, a group of naphthenate, benzoate, p-ethylbenzoic, benzylcarbamoyl, cyclohexanone;

the radical R is alkyl, substituted aryl-position relative to the carbon atom of the carboxylic group:

where R9represents aryl, for example phenyl, and R10is alkyl containing at least 1 carbon atom; for example, group 2-phenylbutyrate.

In the definition of R-COO of carboxylate in accordance with the present invention also includes a mixture of carboxylates with different group R containing from 1 to 30 carbon atoms in accordance with what has been defined above.

A solid component in accordance with the present invention characterize the x-ray spectrum, typical patterns, characterized by the rotational-translational razuporyadochennogo defined as “-the phase in accordance with the usual technical terminology, for example in the publications the solid component is characterized by a very special electronic and coordination environment, which were not previously observed in the catalysts of the type catalysts, Ziegler-Natta containing carboxyl groups. Accordingly, the titanium atoms, in which, I believe, forms the catalytic centre, mainly (at least 80%) have oxidation number +3, and at least 1% of them has a tetrahedral coordination configuration. This last characteristic of the solid component of the catalyst can be observed by spectroscopy electron paramagnetic resonance (EPR), which is sensitive atoms of titanium in the oxidation state +3. Details of this method and its application to systems of the type systems of the Ziegler-Natta can be found in the publication by R. Brant and A. N. Speca “Macromolecules”, vol.20, Nr.11 (1987), pages 2740-2744, the content of which is included in the list of references of this document. In particular, in the analysis of any sample of the solid component of catalyst according to the present invention in its EPR spectrum can be observed the presence of three absorption signals differing in their “g” factors when 1,905, and 1,953 1,968 respectively, with the first two signals are due to the octahedral coordination environment, and the third a tetrahedral coordination environment, which is also rdination configuration. In particular, the authors found that a solid component in accordance with the present invention contains at least 1%, preferably from 2 to 10% titanium in the tetrahedral configuration is shown above. On the contrary, the solid components of catalyst containing Ti and a second metal M of group 4, i.e., Zr, Hf, or any of their mixtures obtained in accordance with the method described in European patent application EP-A 523785, found in the analyses by the EPR method the presence of titanium (+3) essentially completely in octahedral coordination environment, as can be seen in Fig.2. attached to the present description, where the signal having the value “g” 1,968, virtually absent (except for a small slight inflection), while signals having the value “g” 1,905 and 1,946, can be seen very clearly. Although at the present time it is hardly possible to formulate a theory to explain these differences and their impact on the behavior of the corresponding catalysts, it was found that the latter, as it turns out, have more disadvantages than the catalysts of the present invention, both from the point of view of the polymerization activity of olefins, and from the point of view of molecular weight produced sory must be composed of the above-mentioned titanium, magnesium, zirconium, hafnium, aluminum, chlorine, and carboxylate, because of the presence of up to 5 wt.% other components or impurities, which are usually derived from the counterions of the compounds used as precursors, such as alcoholate, bromine, phosphate groups, fluorine and so on, without any flaws. The presence of, preferably not more than 1 wt.%, impurities of other metals present in the compounds of the precursor of the solid catalyst component, it is also possible and does not cause significant changes of its beneficial properties. However, preferred are the solid components of catalyst having the lowest possible amount of impurities, in particular not higher than 2 wt.%.

The amount of titanium contained in the solid catalyst component of the present invention preferably does not exceed 10 wt.%, and more preferably is from 1 to 5 wt.%. The titanium content exceeds 10 wt.%, does not provide any additional advantages from the point of view of the activity of the catalyst, probably due to the fact that the additional amount of titanium present in the solid substance in a form that is inactive or unavailable for interaction with polymerized with the olefin.

In predpochtitel is telesfora in the following ratios in relation to titanium:

M/Ti=0,3-5,0; Mg/Ti=5,0-15,0; Al/Ti=0,1-3,0;

CL/Ti=20,0-50,0; R-COO/Ti=0,5-5,0.

and form at least 99 wt.% of the catalyst. The ratio of carboxylate to the titanium is preferably from 1.0 to 3.0.

As already noted, was found an original and simple method of manufacturing the above solid catalyst component essentially includes four stages.

At the stage of (i) preparing a mixture of an inert fluid, comprising compounds, the precursors of the elements titanium, magnesium, hafnium and/or zirconium. These compounds can be selected from a wide variety of known compounds of these metals, ORGANOMETALLIC and inorganic, as soluble or insoluble in a pre-selected inert liquid, which preferably is a hydrocarbon. At least one of these compounds, preferably at least two or more, preferably compounds of magnesium, hafnium and/or zirconium insoluble in the specified inert liquid to form in her suspension. All connections precursor, which form a mixture, can also be insoluble in the inert liquid selected for stage (i). In a particularly preferred embodiment, at least 50 wt.%, with respect to the total mass, with the above shall comply with the inert liquid so the total concentration of metals (both soluble and insoluble) was in the range of from 0.05 to 2.0 mol/l, more preferably from 0.1 to 1.0.

Compounds of titanium, magnesium, hafnium and zirconium can be selected experts in the art of existing compounds, preferable compounds are most suitable to become soluble by adding carboxylic acid to the next stage (ii). Selection of compounds, the most suitable for this purpose can be made on the basis of solubility parameters of each connection, if known, or by using a simple preliminary tests on the solubility in the presence of selected carboxylic acids. Non-limiting examples of suitable compounds of titanium, hafnium, zirconium and magnesium, both soluble and insoluble, are the chlorides, bromides, alcoholate, hydride,-diketonates,-allowee esters, amides, carbonates, phosphates, mixed connections with these counterions and mixtures of these groups of compounds. The halides, especially the chlorides, and the halides in combination with the alcoholate is particularly preferred.

In a preferred embodiment, vypolneniyasvoey solids or in powdered form.

The mixture of stage (i) can be prepared simply by adding and mixing metal compounds, preferably in granular or powder form, with an inert fluid, in any order. Temperature and pressure are not critical parameters, provided that the liquid remains liquid. Normal temperature and pressure, obviously, are suitable in view of the simplicity of the process. Various metal compounds of the stage (i) is introduced into the mixture in molar ratios, selected based on the desired atomic ratios between the corresponding elements in the solid component obtained at the end of the process. These atomic ratio is not necessarily identical molar ratios of the respective compounds from stage (i), because in accordance with the present invention are possible bias due to the specific conditions used in the process, in particular because of the different solubility of the substances deposited on the stage (iii), which normally can be either more or less than 30%, which is not too impairs the proposed properties of a specific solid catalyst component. Specialists in this field of technology can pre debugging process is from the desired atomic ratios between the elements in the final product.

At stage (ii) of the process in accordance with the present invention the carboxylic acid having the formula (I), added to a heterogeneous mixture of stage (i) to cause almost complete dissolution of all present in her solids. The term “almost complete” in the form in which it is used here in relation to the specified dissolution means that the solution obtained at the end of stage (ii), must be transparent or slightly opalescent and in any case should not contain the sludge solids.

It is obvious that the selected carboxylic acid having the formula (I) has the same group R, and carboxylate R-COO present in the resulting catalyst component. Non-limiting examples of R groups and the corresponding carboxylic acids listed above. However functionalityand group R substituents that are compatible, i.e., inert or no adverse effects in relation to the method of obtaining and use of the proposed solid component, such as halogen, in particular fluorine or chlorine, are not excluded from the total amount of the claims of the present invention.

Carboxylic acid, added at stage (ii), preferably has a relatively large number of atoms ogle same acid, with more than 31 carbon atoms, it is difficult to find on the market, and they do not give special advantages in comparison with acids having from 20 to 31 carbon atoms in the chain.

Stage (ii) of the process in accordance with the present invention is preferably carried out at a temperature higher than room temperature, to provide a fast dissolving solid substances present in the mixture. Observed, that if the dissolution had occurred when temperature was decreased to room is not re-suspension of sediment. Preferably, the temperature of the dissolution was in the range of from 20 to 150°C., more preferably from 70 to 120°C.

Carboxylic acid can be added to a heterogeneous mixture of stage (i) until such time as the solid will not disappear and does not form a clear solution, or you can add a predetermined amount of this acid, and dissolution will be completed at the next stage. The amount of carboxylic acid in each case depends on the nature and quantity of insoluble substances present in the mixture of stage (i). The minimum amount is usually more or less equal to the equivalents of insoluble compounds of metal present in the mixture (equivalent = mol on the valence of the metal). Though the acid and equivalents insoluble compounds were in the range from 0.5 to 2.0, more preferably from 1.0 to 1.5. For example, if a mixture of stage (i) there are 10 moles of insoluble MgCl2and 4 mol insoluble HfCl4a 2 mol of soluble tetrabutyrate titanium in Dean, the amount of carboxylic acid (e.g., 2-ethylhexanoic acid) are preferred in the range from 36 to 54 moles.

The above carboxylic acid can be added to the mixture in pure form or diluted with an inert solvent, preferably the same liquid as in the mixture of stage (i), for example, to improve mixing, if the solid acid, or for more accurate dosing, if you use small amounts.

In the private embodiment of the present invention the carboxylic acid in the desired amount initially added to the mixture of stage (i); the operation is usually carried out at room temperature; the resulting mixture is then subjected to reaction under suitable temperature and pressure until, until you dissolve present in the solids.

Stage (ii) is preferably carried out so that no significant exchange of matter with the environment, for example, in a closed vessel or under conditions of reflux distilled solvent. If reactreporttotal to leave dissolved in the reaction mixture.

At stage (iii) of the process for the preparation of catalyst component in accordance with the present invention, alkylalkoxysilane having the formula (II), enter into reaction with a solution of the above stage (ii) to form the desired solid component of catalyst, which is spontaneously released from the liquid medium in the form of granular sludge. After a drop from 80 to 100% of the titanium present in the solution, in terms of this process is achieved by co-deposition of magnesium and hafnium preferably in an activated form titanium and stable in a wide temperature range. Use as a precipitating agent alkylhalogenide having the formula (II), allows the simultaneous deposition of elements in the form of mixed chlorides or mixed chlorides, carboxylates and recovery of titanium, so that he was present in the solid component, mainly in the oxidation state +3.

Alkylaminocarbonyl having the formula (II) are known and widely used in the polymerization of olefins. The preferred alkylaminocarbonyl are compounds having the formula (II) wherein R’ is a linear or branched aliphatic radical having from 2 to 8 carbon atoms. The index “n” in foraminiferal diethylaluminium, ethylaminoethanol, sibutraminegeneric, dioctyladipate. Alkylaminocarbonyl with non-integer decimal value “n” can be obtained in accordance with known methods by mixing suitable proportions of aluminum chloride and aluminization and/or the corresponding mixed alkylamidoamines with “n” equal to 1 or 2.

Alkylaminocarbonyl having the formula (II) can be added in pure form or in the form of a solution in an inert organic solvent selected from the solvents used for preparing the mixture of stage (i). Adding alkylhalogenide can be performed, while maintaining the reaction mixture in suitable conditions, and checking the concentration of titanium in solution in accordance with one of the known techniques, such as sampling, analysis, or direct definition, colorimetric, or using other techniques suitable for this purpose, until, until you reach the desired level of deposition. In accordance with the preferred implementation for certain reaction systems can pre-define the number of alkylhalogenide, it is sufficient to precipitate, and then add a predetermined number R of the subsequent interaction of the mixture with the formation of the desired precipitate. It was found that in General the minimum number of alkylhalogenide suitable for this purpose can also be determined by calculation according to the equation:

(AlR’nCl(3-n))min.=2/(3-n)·[(4·molit+2·molim+4·Hf+4·Zr-l)at stage (i)+(RCOOH)at stage (ii)].

The number of alkylhalogenide having the formula (II), preferably taken in excess of from 10 to 100% of the minimum number specified as described above. Larger surplus, although possible, but not desirable since it contributes to undesirable side reactions.

Stage (iii) is conveniently carried out at temperatures from 20 to 120°C, its duration can be varied from 0.5 to 8 hours depending on the pre-selected temperature. In a preferred embodiment of alkylalkoxysilane added to a solution of stage (ii), working at a temperature from room temperature (20-25°C) to 60°C, and the resulting mixture is heated and maintained at a temperature of from 50 to 100°C for 45-180 minutes.

Subject to the above terms of a solid component of catalyst obtained as a granular precipitate or powder, preferably with an average particle diameter in the range from 1 to 20 microns.

Thus obtained solid fuel is of liquid and solid substances precluding evaporation of the solvent such as decantation, filtration or centrifugation, preferably wash the solids with the hydrocarbon solvent and, if necessary, to dry.

All manufacturing operations, described above, is best done in a controlled atmosphere of inert gas, for example nitrogen or argon, as aluminiumgie and a solid component of catalyst is sensitive to air and moisture.

In accordance with a particular aspect of the present invention indicated a solid component of catalyst can also be in the form of component deposited on an inert solid material, preferably having a controlled and located in a narrow range of particle size. Suitable inert solid substances are substances which do not change the characteristics of the catalytic part of the above, in particular, the amounts of Ti (+3), relationships between different elements and carboxylate and special coordination characteristics of titanium. Examples of these solids are inorganic solids, such as silicon, aluminum oxide, mixed oxides of silicon and aluminium, titanium oxide, silicates, aluminosilicates, zeolites and similar other products. Polim is used as a carrier. The preferred solids are silicon oxide, aluminum oxide (various forms), amorphous and crystalline aluminosilicates (zeolites). The amount of inert carrier is usually chosen so that it ranges from 50 to 90 wt.% the resulting solid component on the carrier. Such solid components on the carrier is particularly suitable for polymerization processes in the gas phase.

In accordance with the present invention an inert solid carrier, you can type in the desired number in the suspension of inert fluid in stage (i) or, better, on stage (ii). In this case, the solid component is then precipitated on the surface of the inert carrier in stage (iii), which contributes to its homogeneous distribution. Alternatively, the specified media may be impregnated with this solution in stage (ii) and then treated with alkylamidoamines stage (iii) to effect the precipitation of a solid component having a more uniform distribution of the inert carrier.

In accordance with another aspect, the present invention also relates to a catalyst for the (co)polymerization-olefins, in particular ethylene, with a catalyst composed of a solid component to the and 13 of the Periodic table. Aluminiumrail and alkylhalogenide (especially chlorides), which contain from 1 to 10, preferably from 2 to 6 carbon atoms in the alkyl part preferably used as socialization. Among them, preferred are aluminiumrail, such as triethylaluminium, tri-n-butylamine, triisobutylaluminum and tridecylamine. The atomic ratio between aluminum (socializaton) and titanium (solid catalyst component) in the catalysts in accordance with the present invention typically ranges from 2:1 to 500:1, preferably from 5:1 to 200:1, depending on the particular polymerization system and its purity.

The specified catalyst formed in accordance with known techniques by means of contact between the solid component and socialization, preferably in a suitable liquid medium, usually a hydrocarbon, which can also consist of or contain one or more olefins, which are subjected to polymerization. Depending on the characteristics of the polymerization process, which should be applied to the catalyst in accordance with the present invention, the catalyst may be obtained in advance and then introduced into the polymerization reactor, or € catalyst, is not particularly critical and is in a wide range, preferably from 0°C. to the working temperature of the catalyst in a polymerization process. The formation of the catalyst is usually completed almost instantly even at room temperature, although in some cases the contact between the components can last from 10 seconds to 30 minutes depending on temperature before polymerization.

The catalyst in accordance with the present invention it is possible to add one or more additives or additional components to obtain a catalytic system that meets special requirements. It should be considered that the thus obtained catalyst system also fall in the scope of claims of the present invention. Additives or components that may be included in the preparation and/or formulation of the catalyst in accordance with the present invention, is inert solvents, such as, for example, aliphatic and/or aromatic hydrocarbons, aliphatic and aromatic ethers, weakly coordinating additives (base Lewis), is selected, for example, from depolymerizes olefins, ethers, tertiary amines and alcohols, halogenous the like, as well as all other possible components commonly used in the art for the preparation of traditional catalysts for the (co)polymerization of ethylene and other-olefins.

The present invention also relates to processes (co)polymerization-olefins, in which the use of the above catalyst. The catalysts in accordance with the present invention can be used with excellent results in almost all the known processes (co)polymerization-olefins, both in continuous and periodic in one or more stages, such as, for example, processes low (0.1-1.0 MPa), medium (1.0 to 10 MPa) and high (10-150 MPa) pressure, at temperatures from 20 to 300°C, possibly in the presence of an inert diluent. As the regulator of the molecular weight convenient to use hydrogen.

These processes can be carried out in solution or suspension liquid diluent, usually consisting of aliphatic or cycloaliphatic saturated hydrocarbons having from 3 to 12, preferably from 6 to 10 carbon atoms, but which can also consist of a monomer, such as, for example, in the known process sopes, preferably chosen so that the concentration of titanium was in the range of 10-4up to 10-8mol/liter.

Alternatively, the polymerization can be carried out in the gas phase, for example, in a fluidized bed reactor, usually under pressure from 0.5 to 5 MPa and at temperatures from 50 to 150°C, and in this case, it is preferable that a solid component in accordance with the present invention was deposited on the inert carrier substrate, as described above.

The olefins which can be used in the above processes are preferably aliphatic, cycloaliphatic or aromatic olefins containing from 2 to 20, preferably from 2 to 8 carbon atoms, such as ethylene, propylene, 1-butene, 4-methylpent-1-ene, 1-hexene and 1-octene, ethylene-norbornene, styrene. Especially preferred is ethylene, both in terms of processes homopolymerization, and copolymerization processes in which ethylene, however, is the predominant monomer.

In the particular case of bimetallic catalyst in accordance with the present invention can be applied upon receipt of the polymers and copolymer of ethylene with an extremely narrow molecular weight p of the metal catalysts.

The catalyst in accordance with the present invention can be applied with excellent results in the polymerization of ethylene with the formation of linear polyethylene and in the copolymerization of ethylene with propylene or higher-olefins, preferably having from 4 to 10 carbon atoms, to obtain copolymers having different characteristics depending on the specific conditions of polymerization and the number and structure of the-olefin. For example, it is possible to obtain a linear polyethylene with densities from 0,880 to 0,940 and with average molecular weights, preferably in the range of 100000 to 2000000.-Olefins, preferably used as comonomers of ethylene in the production of linear polyethylene of low or medium density (known by the abbreviation ULDPE (polyethylene low density), VLDPE (very polyethylene low density) and LLDPE (LLDPE, linear low density polyethylene), depending on density) are 1-butene, 1-hexene and 1-octene.

The catalyst in accordance with the present invention also can be advantageously used in processes for the copolymerization of ethylene and propylene with education is stable to aging and degradation, or in the ternary copolymerization of ethylene, propylene and a non-conjugate diene having from 5 to 20 carbon atoms, to obtain vulcanizing rubber type EPDM.

Examples of non-conjugate dienes typically used for the preparation of these copolymers are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene and 1,6-octadiene.

The catalyst in accordance with the present invention can particularly advantageously be applied in the processes of high-temperature mortar (co)polymerization-olefins, especially ethylene. These processes are usually carried out at temperatures in the range from 130 to 300°C and pressures from 1 to 25 MPa, preferably from 5 to 20 MPa, in the presence of an inert liquid, necessary to obtain the solution of the resulting polymer at a temperature process. Thus obtain a homogeneous reaction mixture (excluding catalyst), as well as a flexible process that can be easily controlled and which allows you to work at short times of stay and high performance. Preferred liquids from the point of view of their solving ability, and from the point of view of their relatively low toxicity, are aliphatic or cycloaliphatic uglevodorodnym or by evaporating the solvent. More General information on well-known processes of this type is contained in numerous publications, among them we can name, for example, “Encyclopedia of Polymer Science and Engineering”, 2ndedition (1986), volume 6, pages 471-472, John Wiley and Sons Ed.

Since polyolefins, in particular semi-crystalline, are not completely soluble in solvents, the use of relatively high temperatures, preferably from 150 to 230°C, it is necessary for carrying out these processes. The processes carried out in adiabatic or isothermal reactors, depending on the selected technology. However, it is known that in the polymerization processes at such high temperatures average molecular weight of the obtained polymer is significantly reduced, which leads to such high values of melt flow index (RTD) that they are unacceptable for normal processing. The catalysts commonly used in the mortar processes are catalysts based on vanadium, which, however, is not able to provide polyolefins with a satisfactory molecular masses for a variety of applications, limiting thus, the distribution process itself, in spite of the above advantages. In addition, there is the possibility of isatori type catalysts, Ziegler-Natta titanium-based, commonly used in suspension processes are even less suitable than previous catalysts, for use at high temperatures, as produce polyethylene with extremely low molecular weights, suitable for most traditional applications.

Quite unexpectedly it was found that the catalyst in accordance with the present invention allows to obtain polymers and copolymers of ethylene with high values of average molecular weight, also working in the above-mentioned high temperatures, and achieved a much lower value engineers (even one order of magnitude) than when used in the same conditions of traditional catalysts.

The present invention in its many aspects is better illustrated by the following drawings and examples, which are given here with a purely explanatory purposes, in no way limiting the total amount of the claims of the present invention.

In particular, in Fig.1 presents a graph of the first derivative EPR spectrum of solid component of catalyst obtained in accordance with example 1, below; Fig.2 is a graph of the first derivative EPR spectrum of solid components is the max value of the derivative of the absorption spectrum in arbitrary units is indicated on the ordinate axis, the value of “g”-factor, defined below, are indicated on the x-axis.

In each of the above cases, EPR spectra were recorded on EPR spectrometer Bruker ESP E with speed meter HP V, which allows us to estimate the microwave frequency with an accuracy of 1 Hz, which allows you to define the third decimal place in the value of “g”-factor of the electron spin, measured in relation to the spacing of the energy levels of the magnetic component.

In EPR spectroscopy magnetic resonance magnetic field with a frequency (put at a 90° angle to the direction of the magnetic field H in order to induce resonant transition.

The energy of the resonance transition is expressed by the equation g=h/H, where=h/4MS=0,92731·10-20erg·GS; N is a value of the magnetic induction vector, expressed in gausach that allows you to measure the value of “g”-factor in accordance with the methods described, for example, F. E. Mabbs and D. Collison “Electron Paramagnetic Resonance of transition metal compounds”, Elsevier, Amsterdam, (1992).

Quantitative evaluation of Ti(+3) was carried out by comparing the intensities of the EPR signals of the samples of the catalyst is 215;1020spin/g).

Examples

Were applied the following tests and characteristic methods.

Elemental analysis

Quantitative analysis of metal components of the solid component of catalyst (Ti, Zr, Hf, Mg, Al) was performed by the method of plasma spectrometry after wet processing of powdery catalyst on the instrument ICP II Perkin Elmer 1000 (emission spectrometer).

The chlorine content in the same samples was determined using the dynamic potentiometric electrochemical analysis after wet processing of powdery catalyst using a secondary Ag/AgCl electrode (titration of 0.01 M solution of gN3) on the device DOSIMAT 655 METROHM. Curves relative titration registered title-processor 672 METROHM.

X-ray analysis

X-ray diffraction spectra of the samples of the catalyst (in powder form) were recorded on a diffractometer Siemens D500TT using radiation of copper k(=0,15418 nm). Spectra were processed using Siemens Package DIFFRAC-AT.

The melt flow index of

The melt flow index (RTD) associated with mass-average molecular weight of the polymer was measured using standards is alimera within 10 minutes (g/10 minutes).

Sensitivity shift (H. C.) is calculated as the ratio between the engineers at 2,16 kg and engineers with a 21.6 kg, measured in accordance with the above standard method ASTM. This parameter is usually related to the molecular weight distribution.

Reagents and materials

In private versions of the present invention specified in the following examples, we used the following reagents and materials. Products used in the form in which they were received from the manufacturer, except for the cases noted.

Magnesium chloride (gl2, powder, purity >99.4 per cent), manufacturing PECHINEY ITALIA; tetrabutyl titanium (Ti(n-OBu)4, purity >99,90%) manufactured by Du Pont under the trademark TYZOR TMV; hafnium tetrachloride (HfCl4clean <95.5% of (Zr<4,5%), production PECHINEY ITALIA; 2-ethylhexanoate acid (purity to 99.00%), manufacturing BASF; dichloride isobutylamine (purity 99.90 percent), manufacturing WITCO; n-decane, produced Synthesis-(PR) under the trademark SYNTSOL LP 10, purified by passing through a molecular sieve.

Example 1

In a reactor with a capacity of 500 ml were loaded following products in the order given:

70 ml of n-decane; 2.1 g (of 22.3 mmol) MgCl2; 0.7 g (2,07 mmol, 0.7 ml) of tetrabutyl titanium and 0.95 g (2,96 mmol) tetrachloride Mr. ethylhexanoic acid. Thus obtained suspension was heated to 90°C and held at this temperature for 30 minutes in a closed reactor. Thus was obtained a light yellow, slightly opalescent solution.

After cooling the solution obtained as described above, to room temperature, thereto was added dropwise 19.3 g (124,5 mmol, 17,2 ml) dichloride isobutylamine located in 40 ml of n-decane. Thus obtained reaction mixture was heated under stirring to 80°C and kept at this temperature for 2 hours. The obtained dark brown solid was separated from the mother liquor by decantation and then washed with two portions of n-decane in 400 ml.

Got a 3.3 g of the desired solid catalyst component containing 2.7 wt.% titanium (the output of the synthesis in terms of the original tetrabutyl titanium 90%) and is characterized by the following molar ratios between its components:

Hf/Ti=1,6; Mg/Ti=8,5; Al/Ti=1,2; CL/Ti=30,9; (2-ethylhexanoate)/Ti=0,8.

The x-ray spectrum contains typical very broad signals, characteristic for disordered structures “”-type. The amount of titanium in the oxidation state +3 is 97% of the total number of Titan.

Range of EPR p is alil be determined by comparison with the other two signals, having a “g” when 1,905 and 1,953 that 4% titanium (+3) are tetracoordinated environment.

Example 2

In a reactor with a capacity of 5000 ml were loaded following products in the order given:

1000 ml of n-decane; 16 g (168 mmol) MgCl2; 4.8 g (14.1 mmol, 4.8 ml) Ti(n-OBu)4and 2.3 g (7.2 mmol) HfCl4.

Then slowly, with stirring and at room temperature was added to 76.6 g (531 mmol, 84,8 ml) 2-ethylhexanoic acid. Thus obtained suspension was heated to 90°C and held at this temperature for 30 minutes in a closed reactor. Thus was obtained a light yellow, slightly opalescent solution. After cooling the solution to room temperature, thereto was added dropwise 136,7 g (882 mmol, 122 ml) dichloride isobutylamine located in 320 ml of n-decane. Thus obtained reaction mixture was heated under stirring to 80°C and kept at this temperature for 2 hours in a closed reactor. Received purple-pink solid was separated from the mother liquor by decantation and then washed with two portions of n-decane in 1000 ml.

Received 23.1 g of the desired solid component of catalyst containing 2.5 wt.% titanium (the output of the synthesis in terms of the original tetrabutyl titanium, were the; l/Ti=36; (2-ethylhexanoate)/Ti=1,0.

The x-ray spectrum contains typical very broad signals, characteristic for disordered structures ""-type. The amount of titanium in the oxidation state +3 is 98% of the total number of titanium. The content of titanium (+3) in tetrahedral coordination configuration is 2.2% of the total number of titanium (+3).

Example 3

In a reactor with a capacity of 5000 ml were loaded following products in the order given:

800 ml of n-decane; 19 g (200 mmol) MgCl2; 5.7 g (of 16.7 mmol, 5.7 ml) Ti(n-OBu)4and 13.5 g (42.1 mmol) HfCl4.

Then slowly, with stirring and at room temperature was added 105,6 g (732 mmol, 117 ml) 2-ethylhexanoic acid. Then followed the procedure outlined in example 1, and the received light yellow, slightly opalescent solution. After cooling the solution to room temperature, thereto was added dropwise 185,8 g (1199 mmol, 165,9 ml) dichloride isobutylamine located at 433 ml of n-decane. Thus obtained reaction mixture was heated up to 80°C and kept at this temperature for 2 hours in a closed reactor.

Finally, after cooling, received a purple-pink solid precipitate, which was separated from the mother rastet catalyst, containing 1.7 wt.% titanium (the output of the synthesis in terms of the original tetrabutyl titanium amounted to 85%) and characterized by the following molar ratios between its components:

Hf/Ti=3,0; Mg/Ti=13,1; Al/Ti=0,9; Cl/Ti=36; (2-ethylhexanoate)/Ti=2,6.

The x-ray spectrum contains typical very broad signals, characteristic for disordered structures ""-type. The amount of titanium in the oxidation state +3 is 98% of the total number of titanium. The content of titanium (+3) in tetrahedral coordination configuration is 5.0% of the total amount of titanium (+3).

Example 4

In a reactor with a capacity of 500 ml were loaded following products in the order given:

100 ml of n-decane; 3,05 g (32 mmol) MgCl2; 0.95 g (2.8 mmol, 0.95 ml) Ti(n-OBu)4and 4.5 g (14 mmol) HfCl4.

Then slowly, with stirring and at room temperature was added 19.9 g (138 mmol, 22 ml) 2-ethylhexanoic acid. Followed the procedure outlined in example 1, and as a result got a honey-yellow solution. After cooling the solution to room temperature, thereto was added dropwise to 34.7 g (224 mmol, 31 ml) dichloride isobutylamine located in 81 ml of n-decane. Thus obtained reaction mixture was heated ardoe substance was separated from the mother liquor by decantation and then washed with two portions of n-decane in 400 ml.

Got to 7.1 g of the desired solid catalyst component containing 1.6 wt.% titanium (the output of the synthesis in terms of the original tetrabutyl titanium amounted to 85%) and characterized by the following molar ratios between its components:

HF/Ti=4,3; Mg/Ti=9,0; Al/Ti=2,1; Cl/Ti=39,4; (2-ethylhexanoate)/Ti=5,1.

The x-ray spectrum contains typical very broad signals, characteristic for disordered structures ""-type. The content of titanium (+3) in tetrahedral coordination configuration is 6.0% of the total number of titanium (+3).

Example 5

In a reactor with a capacity of 5000 ml were loaded following products in the order given:

1000 ml of n-decane; 17 g (181 mmol) MgCl2; of 5.1 g (15 mmol, 5,1 ml), Ti(n-OBu)4and of 5.24 g (to 22.5 mmol) ZrCl4.

Then slowly, with stirring and at room temperature was added 88,2 g (613 mmol, 97,7 ml) 2-ethylhexanoic acid. Thus obtained mixture was heated to 90°C and held at this temperature for 30 minutes. Thus was obtained a light yellow, slightly opalescent solution.

After cooling the solution to room temperature, thereto was added dropwise 155,6 g (1004 mmol, 139 ml) dichloride isobutylamine located at 363 ml of n-heptane is aces. Received the purple solid was separated from the mother liquor by decantation and then washed with two portions of n-heptane (1000 ml

Got to 26.9 g of the desired solid catalyst component containing 2.4 wt.% titanium (the output of the synthesis in terms of the original tetrabutyl titanium 90%) and is characterized by the following molar ratios between its components:

Zr/Ti=2,1; Mg/Ti=9,3; Al/Ti=,1; Cl/Ti=30,5; (2-ethylhexanoate)/Ti=2,8.

The x-ray spectrum contains typical very broad signals, characteristic for disordered structures ""-type. The content of titanium (+3) in tetrahedral coordination configuration is 4.3% of the total number of titanium (+3).

Example 6 (comparative)

In order to compare the solid catalyst component was prepared in accordance with the method, based on the use of pre-prepared carboxylates of metals, as described in the patent EP-A 523785 noted above.

1) preparation of a solution gl(2-ethylhexanoate)

11.4 g (to 107.7 mmol) MgCl2suspended in 100 ml of n-decane, loaded into the reactor with a capacity of 500 ml and Then slowly, under stirring and at room temperature add 46.6 g (323 mmol, 51,6 ml) 2-ethylhexanoate through the suspension of nitrogen for 5 hours.

The result is 104 ml clear light yellow solution containing the following concentrations of dissolved substances: MD=1034 mmol/l, Cl=786 mmol/l, 2-ethylhexanoate acid=3102 mmol/L.

2) preparation of a solution fl2(2-ethylhexanoate)2

In a reactor with a capacity of 500 ml load of 20 g (of 62.4 mmol) HfCl4suspended in 150 ml of n-decane. Then slowly, with stirring and at room temperature add 18 g (of 124.8 mmol, 19.9 ml) 2-ethylhexanoic acid.

The reaction mixture is brought to a temperature of 100°C., and present in a mixture of chlorine is partially removed by bubbling through the suspension of nitrogen for 5 hours. Not all of the solid dissolves, and therefore must be filtered through a porous membrane. The result 131 ml clear light yellow solution containing: Hf=95,4 mmol/l, Cl=174,8 mmol/l, 2-ethylhexanoate acid = 191 mmol/L.

3) preparation of a solution il2(2-ethylhexanoate)2

4.3 g (22.7 mmol, 2.5 ml) iCl4dissolved in 100 ml of n-decane, loaded into the reactor, with a capacity of 500 ml and Then slowly, under stirring and at room temperature add 6.5 g (45,1 mmol, 7.2 ml) 2-ethylhexanoic acid. The reaction mixture is brought to a temperature of 100°C, and price transparent dark green solution containing the following concentrations of dissolved substances: Ti=330 mmol/l, Cl=650 mmol/l, 2-ethylhexanoate acid = 660 mmol/L.

4) preparation of solid catalyst component

In a reactor with a capacity of 500 ml download the following products in the order given:

to 150 ml of n-decane;

to 20 ml of a solution gl(2-ethylhexanoate), prepared as described above and containing 6.5 g (20,7 mmol) MD, of 8.95 g (62 mmol) 2-ethylhexanoic acid and 0.56 g (15.8 mmol) of chlorine;

is 25.2 ml fCl2(2 ethylhexanoate)2prepared as above and containing of 0.44 g (2.5 mmol) Hf, 0.16 g (4.5 mmol) of chlorine and 0.72 g (5 mmol) 2-ethylhexanoic acids;

- 5,7 ml Til2(2 ethylhexanoate)2prepared as above and containing of 0.44 g (2.5 mmol) of Ti, of 0.13 g (3.7 mmol) of chlorine and 0.54 g (3,76 mmol) 2-ethylhexanoic acid.

Forms a transparent mixture, which is at a temperature of about 30°C is added dropwise to 17.5 g (113 mmol) of dichloride isobutylamine located in 42 ml of n-decane. By the end of the addition the temperature is raised to about 80°C. and the mixture was kept at this temperature for 2 hours under stirring. Formed finely suspended reddish-brown solid, which is separated from matonoha component of the catalyst, containing 2.8 wt.% titanium (the output of the synthesis in terms of initially introduced titanium amounted to 85%) and characterized by the following molar ratios between its components:

HF/Ti=1,3; MD/Ti=9,2; Al/Ti=1,7; CL/Ti=31,1; (2-ethylhexanoate)/Ti=0,6.

On the basis of the x-ray spectrum of the solid substance has been proven that it has a disordered structure “”-type. The amount of titanium in the oxidation state +3 is 97%.

Range of EPR thus obtained solid component of catalyst are shown in Fig.2. The marked absence of a signal at g=1,968 present in the spectrum shown in Fig.1, which belongs to the solid component prepared in accordance with example 1 of the present invention.

Example 7 (comparative)

The purpose of the comparison was prepared solid catalyst component based on one of titanium, instead of a combination of titanium and hafnium. Used the same way in accordance with the present invention.

In a reactor with a capacity of 500 ml were loaded following products in the order given:

100 ml of n-decane; 5.6 g (58.8 mmol) gCl2and 1.3 g (3.8 mmol, 1.3 ml) Ti(n-OBu)4. Then slowly, with stirring and at room temperature dopaminergically at this temperature for 30 minutes in a closed reactor. By the end of the procedure in suspension in the form of fine sediment remained undissolved about 15 wt.% of the initial number of MgCl2. After cooling the mixture thus obtained to room temperature, it was introduced into the reaction dichloride isobutylamine without removing solid material remaining undissolved in the previous phase. In particular, to the mixture was added to 44.6 g (288 mmol, 39,8 ml) dichloride isobutylamine, located in 104 ml of n-decane, and then heated the mixture to 80°C and kept at this temperature for 2 hours.

The obtained pale-pink solid was separated from the mother liquor by decantation and then washed with two portions of n-decane in 400 ml. Got to 6.1 g of solid catalyst component containing 2.6 wt.% titanium, while the output of the synthesis in the calculation of the original Titan was 85%, and is characterized by the following molar ratios between its components:

MD/Ti=12,6; Al/Ti=2.7; the CL/Ti=34,4; (2-ethylhexanoate)/Ti=1,9.

The amount of titanium in the oxidation state (+3) is 98%.

Examples 8-16 (copolymerization of ethylene in solution) Various experiments on the polymerization of relatively homogeneous conditions in relation to each other were produced using components katalysatoren mixing device, manometer and devices required for supplying gaseous reactants were loaded following products in the order listed: 2.0 liters of anhydrous n-decane as a solvent, triethylaluminium, acting as socialization and filter impurities, 74 ml of 1-hexene as co monomer, and a solid component of catalyst. The temperature was raised to the desired level, usually between 210 and 220°C, and was quickly introduced ethylene, while the liquid was stirred until then, until reaching the desired pressure.

The copolymerization reaction was continued for 5 minutes and then terminated by adding ethanol, saturated with carbon dioxide (16 g (350 mmol), and 20 ml of ethanol and 10 g (230 mmol) of carbon dioxide (dry ice)).

The polymer is precipitated with methanol is added and again washed with methanol. Then it was dried in a stream of air, weighed and characterized by measuring the density, melt flow index (RTD) and sensitivity to a shift in the ways described.

Values, conditions and results of experiments on the polymerization schematically summarized in the table below, the columns of which consistently indicated for each example: the example used the example of the preparation of the solid is x, the temperature and pressure of the polymerization, the amount of the obtained polymer and its density, engineers and sensitivity to shear, and, finally, the catalytic activity per titanium.

Examples 15 and 16 and comparative examples.

Example 17

In a reactor with a capacity of 5 l were loaded following products in the order given:

2000 ml of anhydrous n-decane, 57 mg (0.5 mmol, of 0.07 ml) of triethylamine, 45 g (536 mmol, 66 ml) of 1-hexene and 12.2 mg of solid component of catalyst of example 1, equivalent to 0.33 mg (6,9 mmol) of Ti.

The polymerization temperature was raised to 183°C and pressure up to 1.3 MPa by introducing ethylene. The reaction was continued for 5 minutes and then stopped by adding a mixture containing 20 ml of ethanol and 10 g of carbon dioxide (dry ice).

As a result received 63 g of polyethylene with activity 188 kg of polyethylene per mole of titanium in the solid component. Thus obtained polymer had the following properties:

Engineers (2,16 kg) = 0,02 DG/min, sensitivity to shear 43,4; density = 0,9244 g/ml.

Example 18

In a reactor with a capacity of 5 l were loaded following products in the following order:

2000 ml of anhydrous n-decane, 57 mg (0.5 mmol, of 0.07 ml) of triethylamine, 35 g (417 mmol, 52 ml) 1-hexenenitrile raised to 218°C, and the pressure to 1.3 MPa by introducing ethylene. Then followed the procedure described above in example 17. The result obtained 48 g of polyethylene with exit 59 kg polyethylene per mole of titanium in the solid component. Thus obtained polymer had the following properties:

Engineers (2,16 kg) = 0.3 g/10 min; sensitivity shift = 34,5; density = 0,9312 g/ml.

Example 19

In a reactor with a capacity of 5 l were loaded these products in this order: 2000 ml of anhydrous n-decane, 57 mg (0.5 mmol, of 0.07 ml) of triethylamine, 67 g (598 mmol, 94 ml) of 1-octene and 44.4 mg of solid component of catalyst of example 1, equivalent to 1.2 mg (25,0 µm) Ti.

The polymerization temperature was raised to 220°C., and the pressure to 1.45 MPa by introducing ethylene. Then followed the procedure described above in example 17. The result has been 55 g of polyethylene with access to 45.8 kg of polyethylene per mole of titanium in the solid component. Thus obtained polymer had the following properties:

Engineers (2,16 kg) = 0,76 DG/min, sensitivity to shear = 37,4; density=0,9275 g/ml.

Example 20

In a reactor with a capacity of 5 l were loaded following products in the order given:

2000 ml of anhydrous n-decane, 99 mg (0.5 mmol, 0,07 ml) triisobutylaluminum, 50 g (595 mmol, 75 ml) of 1-hexene and 37 mg totoymola to 173°C. pressure up to 1.4 MPa by introducing ethylene. Then followed the procedure described above in example 17. The result has been 85 g of polyethylene with the release of 86 kg of polyethylene per mole of titanium in the solid component. Thus obtained polymer had the following properties:

Engineers (2,16 kg) = 0.1 g/10 min, the sensitivity shift = 30,4; density = 0,9087 g/ml.

Claims

1. A solid component of catalyst for the (co)polymerization-olefins, comprising at least 95 wt.% titanium, magnesium, at least one metal selected from hafnium, zirconium, aluminum, chlorine, and R-COO of carboxylate, in the following molar proportions:

M/Ti=0,1-10,0; Mg/Ti=1,0-20,0; Al/Ti=0,01-6,0;

CL/Ti=2,0-70,0; R-COO/Ti=0,1-10,0,

where R is aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing from 1 to 30 carbon atoms;

M is a metal selected from hafnium and zirconium or one of their mixtures,

characterized in that at least 80% of the titanium is in the oxidation state +3 and, in addition, at least 1% of the specified titanium in oxidation state +3 has a tetrahedral coordination configuration.

2. A solid component under item 1, wherein the following mo the Torah under item 1 or 2, in which M is hafnium.

4. A solid component of catalyst according to any one of paragraphs.1-3, in which at least 90% of the titanium is in the oxidation state +3 and from 2 to 10% of the specified titanium has a tetrahedral coordination configuration.

5. A solid component according to any one of paragraphs.1-4, in which the number of carbon atoms in the radical R of the specified carboxylate ranges from 6 to 15.

6. A solid component according to any one of paragraphs.1-5, in which the titanium content not greater than 10 wt.%.

7. The method of preparation of the solid component of catalyst for the (co)polymerization-olefins, comprising at least 95 wt.% titanium, magnesium, at least one metal selected from hafnium, zirconium, aluminum, chlorine, and R-COO of carboxylate, in the following molar proportions:

M/Ti=0,1-10,0; MD/Ti=1,0-20,0; Al/Ti=0,01-6,0;

Cl/Ti=2,0-70,0; R-COO/Ti=0,1-10,0,

where R is aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing from 1 to 30 carbon atoms;

M is a metal selected from hafnium and zirconium or one of their mixtures,

characterized in that the method comprises the following sequence of stages: (i) preparation of a mixture of at least one compound of magnesium, link is oasa of the inert organic liquid, which is insoluble in at least one of said components; (ii) preparation of essentially transparent solution by adding to the said mixture of stage (i) a sufficient number of carboxylic acid having the formula

R-COOH (I)

where R is aliphatic, cycloaliphatic or aromatic hydrocarbon radical containing from 1 to 30 carbon atoms,

and maintaining the mixture in suitable conditions of pressure and temperature to achieve essentially complete dissolution of all insoluble compounds; (iii) adding to the solution obtained in stage (ii). alkylhalogenide, which may be represented by the following General formula (II):

AIR’nCl(3-n)(II)

where R' is a linear or branched alkyl radical containing from 1 to 20 carbon atoms;

n is a decimal number whose values range from 0.5 to 2.5,

in a quantity at least sufficient to make the loss of at least 70%, preferably from 80 to 100% of the titanium present in the solution in this stage (ii), precipitated in the form of solid compounds, and (iv) the separation of the solid matter deposited on the stage (iii), from the remaining liquid with the purpose of obtaining a decree of the re one metal, selected from hafnium, zirconium, aluminum, chlorine, and R-COO of carboxylate, in the solid component of catalyst are 98 to 100 wt.%.

9. The method according to p. 7 or 8, wherein said metal M is hafnium, and this group R carboxylic acid R-COOH includes from 6 to 15 carbon atoms.

10. The method according to any of paragraphs.7-9, in which the specified liquid used to prepare the mixture of stage (i) are selected from aliphatic, cycloaliphatic or aromatic hydrocarbons.

11. The method according to any of paragraphs.7-10, in which at least two compounds selected from compounds of magnesium, hafnium and/or zirconium in stage (i) is not soluble in the specified inert liquid to form in her suspension.

12. The method according to any of paragraphs.7-11, in which at least 50 wt.% these compounds stage (i) is not soluble in pre-selected inert liquid.

13. The method according to any of paragraphs.7-12, in which these compounds on stage (i) is mixed with an inert fluid at a total concentration of metals (as in a soluble state, and insoluble) from 0.05 to 2.0 mol/L.

14. The method according to any of paragraphs.7-13, in which the magnesium and at least one metal selected from hafnium and zirconium, is introduced into the mixture of stage (i) in the form of chlorides in formerror dissolution stage (ii) is from 70 to 120°C.

16. The method according to any of paragraphs.7-15, in which the specified stage (ii) carry out so that no significant exchange of substances with the environment.

17. The method according to any of paragraphs.7-16, in which in stage (iii) the index n of the specified alkylhalogenide having the formula (II) represents a decimal number average of from 0.9 to 2.1.

18. The method according to any of paragraphs.7-17, in which the number specified alkylhalogenide used in this stage (iii), exceeds 1.1 to 2.0 times the minimum amount defined by the equation

(AlR’nCl(3-n))min=2/(3-n)· [(4· malic+2· molimed+4· Hf+4· Zr-l)· stage(i)+(moles· R)· stage(ii)].

19. The method according to any of paragraphs.7-18, in which in stage (iii) alkylhalogenide added to a solution of stage (ii) from room temperature (20-25°C) to about 60°C, and the resulting mixture was heated and maintained at temperatures of from 50 to 100° C for 45 to 180 minutes

20. A solid component of catalyst according to any one of paragraphs.1-6, characterized in that it is obtained by the method according to any of paragraphs.7-19.

21. A solid component of catalyst according to any one of paragraphs.1-6 and 20, consisting of 98 to 100 wt.% titanium, magnesium, at least one metal, the g src="https://img.russianpatents.com/chr/945.gif" border="0">-olefins, including socialization consisting of a hydride or ORGANOMETALLIC compound of a metal of the 1st, 2nd or 13th group of the Periodic table and a solid component in contact with each other, characterized in that the solid component consists of a solid component of catalyst according to any one of paragraphs.1-6, 20 and 21.

23. The catalyst according to p. 22, which specified socialization selected from aluminization, which contain from 1 to 10, preferably from 2 to 6, carbon atoms in the alkyl part.

24. The catalyst p. 23, in which the atomic ratio between aluminum (socializaton) and titanium (solid catalyst component) is in the range from 2:1 to 500:1, preferably from 5:1 to 200:1.

25. The method of (co)polymerization-olefins comprising the polymerization of at least one-olefin is continuously or intermittently in one or more stages at low (0.1 to 1.0 MPa), average (1.0 to 10 MPa) and high (10-150 MPa) pressure, at temperatures from 20 to 300°C., possibly in the presence of an inert diluent, in the presence of a suitable catalyst, characterized in that the latter represents a catalyst according to any one of paragraphs.22-24.

26. Method () polymerizations (co)polymerization under item 25 or 26, in which ethylene is subjected to polymerization with the formation of linear polyethylene or copolymerization with-olefins having from 3 to 10 carbon atoms.

28. The method of (co)polymerization according to any one of paragraphs.25 to 27, characterized in that it is carried out in a solution of inert solvent at a temperature of from 130 to 300°C and a pressure of from 1 to 25 MPa.

29. The method of (co)polymerization according to any one of paragraphs.25-28, wherein said inert solvent is selected from aliphatic or cycloaliphatic hydrocarbons having from 6 to 10 carbon atoms.

30. The method of (co)polymerization according to any one of paragraphs.25-29, in which the polymerization temperature is from 150 to 230°C.



 

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The invention relates to methods of producing polymers-olefins, effectively reducing the hydrodynamic resistance of hydrocarbon liquids and can be used for transporting petroleum products in pipelines

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

The invention relates to the components of the catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and at least one 1,3-W, which forms complexes with anhydrous magnesium dichloride in an amount of less than 60 mmol per 100 g of MgCl2and without substitution reactions with TiCl4or reacting in the amount less than 50 mol%, and at least one ester of mono - or polycarboxylic acid, and 1,3-diesters selected from compounds of the formula (II)

where the group RIIIidentical or different, represent hydrogen or C1-C18hydrocarbon group; groups of RIVidentical or different, have the same meaning as RIIIexcept that they cannot be hydrogen; each of the groups RIII- RIVmay contain heteroatoms selected from Halogens, N, O, S and Si, and the radicals RVidentical or different, are selected from the group consisting of hydrogen; Halogens, preferably C1 or F; C1-C20alkyl radicals with a straight or branched chain; C3-C20cycloalkyl,6e radicals Rvcan be connected to each other to form a condensed cyclic structures, saturated or unsaturated, optionally substituted, RVIradicals selected from the group consisting of halogen, preferably C1 or F; C1-C20alkyl radicals, linear or branched; C3-C20cycloalkyl, C6-C20aryl, C7-C20alkalinic and C7-C20Uralkalij radicals; the radicals RVand RVIoptionally contain one or more heteroatoms as substitutes for carbon or hydrogen atoms, or both

The invention relates to a component of a solid catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and an electron donor selected from substituted succinates formula

The invention relates to a solid titanium catalyst component for use as a catalyst in the production of homopolymers or copolymers of olefins and to a method for producing a solid titanium catalyst component

The invention relates to methods for macromolecular higher poly-alpha-olefins, in particular polyacene, and catalysts for carrying out the method

The invention relates to methods for macromolecular higher poly-alpha-olefins and catalysts for carrying out the method

The invention relates to a solid catalyst component obtained by a process comprising a stage of bringing (a) a liquid magnesium compounds into contact with (b) a liquid compound of titanium in the presence of (C) organosilicon compounds having inactive hydrogen in an amount of from 0.25 to 0.35 mol per 1 mol of compound of magnesium (a) increasing the temperature of the obtained contact product (i) to a temperature of from 105 to 115oWith and holding the contact product at this temperature

The invention relates to a method for producing polyethylene by polymerization of ethylene at elevated temperature and pressure in the presence of a catalyst consisting of zirconocene and socializaton - methylalumoxane, while the polymerization of ethylene is carried out at a temperature of 100-150oC, a pressure of 4-8 bar in the presence of a catalyst containing as zirconocene a compound selected from the group including rat-dimethylsilane - bis-1-(2-methyl-4-phenylindane)zirconiated, rat - dimethylsilane-bis-1-(2-metalcrafter)zirconiated, rat - dimethylsilane-bis-1-(2-methyl-4,5-benzhydryl)zirconiated
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