CS262451B1 - Catalyst for 1-alkenes polymerization - Google Patents

Abstract

The solution relates to a supported catalyst for the polymerization of 1-alkenes. The catalyst formed by successively depositing on an inert inorganic silicon or aluminum oxide at least one organic aluminum compound and optionally magnesium, at least one transition metal compound of group 4a or 5a of the periodic table and optionally at least one organic magnesium compound is phlegmatized with 0.5 to 50 t by weight of a paraffinic hydrocarbon with a melting point of 25 to 150 °C, which is deposited either together with the active components of the catalyst or separately or is formed on the catalyst by prepolymerization of 1-alkenes.

Description

The invention relates to single-phase supported catalysts for the polymerization and copolymerization of 1-alkenes, in which oxides are used as a support and saturated hydrocarbons are used as a protective layer.

Polymers and copolymers of 1-alkenes are usually prepared using catalyst systems based on transition metals, which can be supported and are usually activated by reaction with a cocatalyst - an alkyl compound - just before entering the reactor or in the polymerization device. These catalysts show high activity, relative to the transition metal, and easily copolymerize higher 3-alkenes. The type of transition metal and ligands bound to the transition metal can influence the polymerization activity, molecular weight distribution, rheological and mechanical-physical properties of the polymers.

By adding electron donor substances, propene can be polymerized and 1-alkenes can be made into stereoregular polymers.

The source of serious technological complications is the activation of the catalyst with an organometallic compound immediately before entering the reactor or in the reactor. The concept of these catalysts is based on a precursor of suitable composition, which is not polymerizingly active. The interaction with the organometallic compound creates a polymerizingly active system, which quickly loses activity without the presence of a monomer and/or the presence of a monomer is necessary for the formation of an active center. Therefore, this step is carried out only in the polymerization reactor. This means that two components are dosed into the reactor - a catalytic precursor - usually in the form of a powder - and a solution of the organometallic. The free organometallic initiates the oligomerization of olefins, which causes undesirable deposits on the inner walls of the polymerization device. By reacting with atmospheric oxygen and impurities of the system, the access (diffusion) of which is practically impossible to prevent, the organometallic decomposes to aluminum oxide, which contributes to the further formation of deposits. Deposits of oligomers with alumina are very difficult to remove and it is often necessary to discard narrow profiles and replace them with new ones (e.g. recycle coolers in gas phase polymerization).

The presence of free organometal also negatively affects the kinetics of polymerization, because the permanent contact of the organometallic compound with active centers leads to adsorption, thereby reducing the number of free centers capable of polymerization, and to undesirable mechanical changes in the centers (reduction of the transition metal), which results in a decrease in activity and an inappropriate distribution of polymer particle size - a high content of dust and particles with a diameter below 0.1 mm.

Another factor that significantly affects the properties of polymers is the quality of anchoring the active component on the support. In most existing catalytic systems, perfect immobilization of reaction products on the surface of the support is not ensured, which allows mutual migration of individual components and thus further undesirable reactions leading to the disappearance of active centers. Catalytic systems based on transition metals with additional activation are described, for example, in patent documents US 4 302 566, US 3 787 384, US 4 148 754, US 4 063 009, US 4 173 547, '

US 4,490,514 A, GB 1,484-254, GB 2,099,834.

In recent years, single-phase catalytic systems based on transition metals of groups 4a and 5a of the periodic table have been developed. In the polymerization of 1-alkenes on single-phase catalysts based on titanium, vanadium and zirconium, complications with the dosing of cocatalysts are eliminated, deposits do not form on the walls of the polymerization device and the polymer obtained has the desired particle morphology. Single-phase catalytic systems based on titanium are described, for example, in patent documents BE 884 513, BE 886 420, JA 5 200 880.

Single-phase catalytic systems are highly active in the polymerization of 1-alkenes and, due to the small amount of organometallic compounds, are easily deactivated by reaction with impurities. The reactivity of these substances can be significantly reduced by covering the surface with a layer of inert solid and thus creating an effective diffusion barrier. This phlegmatization of the surface is very effective and allows the protection of highly active substances for an arbitrarily long time (depending on the thickness of the protective layer). During the polymerization itself, the catalyst must be in its active form, the rate of diffusion of the monomer to the active centers must not be reduced. Therefore, it is possible to realize a protective layer from a substance with a melting point between the ambient temperature and the polymerization temperature. In practice, saturated hydrocarbons and their mixtures can be used.

Patent document US 4 200 715 describes the dispersion of a supported catalyst in a solid phase, formed by mixing paraffin wax with a liquid low molecular weight hydrocarbon. The catalyst modified in this way is resistant to the diffusion of impurities and can be dosed into the reactor practically without inert gas. Dispersion is carried out only with the finished catalyst, the possibility of changing the chemical parameters of the catalyst by anchoring the paraffin phase at the stage of applying the catalytic components is not used. Patent document EP 159 736 describes the modification of a single-component unsupported catalyst by coating it with a layer of viscous mineral oil. The resulting loose powder is characterized by long-term storage stability and stability of polymerization activity.

A protective hydrocarbon layer can also be formed on the catalyst surface by prepolymerization of 1-alkene. This method has other advantages. Active transition metal-polymer bonds are formed, which are more stable than transition metal-alkyl bonds. Furthermore, a polymer with a different composition can be formed, thus modifying the properties of the final polymer.

Prepolymerization with the aim of improving the activity of the catalyst on a MgCl2 support and resistance to abrasion is the subject of patent document FR 2 529 211. Elimination of stickiness of polymer particles and formation of lumps in the reactor by means of prepolymerization is the subject of patent documents EP 102 895 (support based on _MgCl2 and AlCl2) and HO 8 505 111 A (unsupported catalyst). Patent document GB 2 154 242 A describes a reduction in the content of fine polymer particles after prepolymerization of a small amount of ethylene, optionally with an admixture of 1-alkenes. According to patent document JA 59 215 301, 1-butene or 4-methyl-1-pentene is prepolymerized on a highly active unsupported titanium catalyst, after which either part of the polymer formed is dissolved and removed or another monomer is prepolymerized. During the polymerization of ethylene itself and copolymerization with 1-alkenes, polymers with high bulk density are formed at a higher rate.

The method of producing catalysts based on transition metals and oxide supports is described in Czech Patents No. 256,961 and No. 259,736. This invention relates to a method of phlegmatizing this type of catalysts with the aim of improving polymerization parameters.

The subject of the invention is a catalyst for the polymerization and copolymerization of 1-alkenes, formed by successive anchoring onto a porous oxide of elements of group 3b and/or 4b of the periodic table at least one organic aluminum compound and optionally magnesium, at least one titanium and/or vanadium compound and optionally at least one organic magnesium compound, which contains 0.5 to 50 wt. % of a paraffinic hydrocarbon with a melting point of 25 to 150 °C.

In particular, the invention relates to catalysts containing paraffinic hydrocarbons which are formed by applying a paraffinic hydrocarbon in a mixture with some catalyst component or onto an active catalyst and to catalysts in which the paraffinic hydrocarbon is formed on the active catalyst by prepolymerization of 1-alkene.

For catalysts useful for producing polymers and copolymers according to the present invention, a suitable support is silica and/or alumina with a specific surface area of 50 to 500 ^{m 2} /g, a pore volume of 0.5-3 ml/g, having hydroxyl groups bound to the surface, the number of which can be varied by the dehydration temperature.

This is done by blowing through the carrier layer with a stream of dry nitrogen or air. The procedure is that the temperature is first gradually and slowly increased to 200 °C so that water vapor can escape without disturbing the carrier structure or condensing in the cooler parts of the device. Dehydration of the carrier is usually carried out for 4 hours at a selected temperature in the range of 200 to 850 °C. Cooling of the carrier is done with a stream of nitrogen, the water and oxygen content of which is lower than 1 ppm,

In a hydrocarbon solvent environment or in the gas phase, the support is then treated with at least one organometallic compound, e.g. trialkyls, dialkyl hydrides, dialkyl halides.

I alkyl dihalides or. dialkyl alkoxides of aluminum, or dialkyls of magnesium, whereby the organometallic compound is firmly anchored. For uniform application, the carrier suspension or carrier layer must be stirred intensively, it is preferable to carry out the interaction in a fluidized bed. The temperature during the interaction can vary within a wide range depending on the vapor pressure of the organometallic compound, it is preferable to carry out the reaction at a temperature of 10 to 70 °C, preferably at ambient temperature.

In a further step, at least one group 4a or 5a transition metal compound, e.g. a halide, oxyhalide, haloalkoxide or cyclopentadienyl derivative of this metal, is applied to the support with the anchored organometallic compound. The reaction of the product formed by the interaction of the organometal with the hydroxyl groups of the support with the transition metal compound can be carried out preferably in a hydrocarbon medium or by direct contact of the vapors of the transition metal compound with the solid phase of the intermediate, preferably at room temperature.

By chemically binding the organometal to the free hydroxyl groups of the substrate, modification of its reducing and alkylating capabilities and simultaneous immobilization on the surface is achieved. By fixing the organometal on the surface of the support, choosing the ratio of the organometal compound to the hydroxyl groups and the ratio of the transition metal compound to the organometal compound, the formation of optimal active centers on the surface of the support is achieved, which have the ability to polymerize 1-alkenes. Perfect anchoring of the components in the pores of the support and on its surface is a condition for high and long-term stable activity of the catalyst, good handling of the powder catalyst and its long-term storage.

According to AO No. 259 736, the properties of a single-phase catalyst can be further significantly improved by applying another component - an organomagnesium compound - dialkylmagnesium. This layer has only slight alkylating and reducing effects and serves primarily to protect the active centers in the pores of the carrier from penetrating impurities during the final phase of production, storage, transportation and dosing of the catalyst. The conditions and method of applying the organomagnesium compound are the same as for the previous components.

A significant step in the preparation of the catalyst according to the present invention is the application of a paraffinic hydrocarbon to the surface of the catalyst particles. It is important that the melting point of the paraffinic hydrocarbon lies between the polymerization temperature and the maximum normal temperature of the environment in which the catalyst is produced, stored and transported. Paraffin with a melting point of 50 °C to 70 °C, atactic polypropylene or other saturated hydrocarbons with a suitable melting point can be used. The presence of double bonds and heteroatoms in the paraffinic hydrocarbon chains is undesirable, as it reduces the activity of the catalyst. Low molecular weight impurities of the electron donor type have the same negative effect. The paraffinic hydrocarbon can be applied to the finished catalyst, suspended in a hydrocarbon solvent, or simultaneously with the last component of the catalyst; i.e. either in a mixture with a transition metal compound, or with an organomagnesium compound, if the latter is used. The paraffinic hydrocarbon is applied so that its content is 0.5 to 50 wt% of the catalyst, preferably 1 to 10 wt%. The principle of action of the paraffinic hydrocarbon is to coat the catalyst particles and prevent the diffusion of impurities during isolation, storage, transport and dosing of the catalyst to the active centers. The creation of a diffusion barrier on the catalyst surface further stabilizes the catalytic system in the absence of monomer, the reactivity of the catalyst components is significantly reduced and a large part of the active centers is formed only after the paraffinic hydrocarbon has melted in the reactor.

A successful step in the preparation of the single-phase catalyst according to the present invention is the dehydrating of the hydrocarbon solvent by a stream of inert gas, by evacuation or by raising the temperature above the boiling point of the solvent.

The polymerization of 1-alkenes according to the invention on a single-phase catalyst can be carried out in a mechanically or pneumatically stirred fluidized bed. The polymerization is carried out at a temperature of 50 to 120 °C; lower temperatures are advantageous for the polymerization of higher 1-alkenes with a lower softening point, higher temperatures can be used for the homopolymerization of ethylene and the copolymerization of ethylene with 1-alkenes. The polymerization temperature must be maintained 5 to 10 °C below the melting point of the polymer to avoid sticking.

particles. The polymerization pressure is usually 0.5 to 4.0 MPa. The optimum is 1.8 to 2.2 MPa, because at lower monomer pressures the catalyst productivity is lower (it is directly proportional to the monomer pressure), at pressures higher than 2.2 MPa the costs of purchasing and operating pressure vessels and of compressing working media increase. It is advantageous to carry out the polymerization at constant pressure, temperature and concentration of individual components with continuous dosing of the catalyst, monomer mixture, hydrogen as a chain transfer agent and with continuous product withdrawal. A batch process can also be implemented, but it is not economically advantageous.

The molecular weight can be controlled by dosing hydrogen. Without hydrogen, ultra-high molecular weight polymers (UHMW) are formed, and as the hydrogen content increases, the melt index of the polymer decreases sharply.

The usual hydrogen content in the monomer mixture for injection and blow molding types is 2 to 5% by volume. At hydrogen contents of 10 to 20% by volume, highly fluid polymer types (fiber types) are achieved.

The catalyst dosage can be controlled using the instantaneous polymerization rate (polymerization heat generated). The catalyst is powdered, has good flowability, and retains the properties of the original carrier even with a relatively high content of active catalyst components (including solvent and paraffinic hydrocarbon) - up to 50% by weight.

During polymerization, spherical polymer particles are formed, which are similar in shape to the initial catalyst particles, and therefore to the carrier. The magnification factor is 20 to 50 times, during polymerization compact particles of 0.5 to 5 mm in size are formed, depending on the polymerization time (in the discontinuous process) or the residence time (in the continuous process). The usual polymerization time or residence time is 1 to 8 hours, most often 2 to 6 hours. With shorter polymerization times, the ash and catalyst residue content in the polymer is higher, the reactor productivity is high, on the contrary, with longer polymerization times the polymer purity improves and the reactor productivity decreases.

The catalyst is deactivated at the reactor outlet with air, steam or carbon monoxide, and the catalytic residues do not need to be washed. The polymer is stabilized with conventional stabilizers against UV radiation and oxidation at higher temperatures; due to the high activity of the catalyst and therefore the low content of catalytic residues, a small amount of stabilizers is sufficient. Due to the high bulk density of the powder and large particles, granulation is not necessary, which eliminates one thermal stress.

The advantage of the production of polyolefins using the catalyst according to the present invention is that an active catalytic system is used, which does not require further activation in the polymerization device. Fixation of the components to the carrier and additional application of a paraffinic hydrocarbon prevent mutual migration of the catalyst components and thus undesirable side reactions leading to the disappearance of active centers. Coating the catalyst particles with a solid paraffinic hydrocarbon prevents the diffusion of impurities to the active centers in the period between the production of the catalyst and the actual polymerization in the reactor. Fixed active centers in the pores of the carrier allow polymerization to be carried out at a high speed without the formation of undesirable molten polymer lumps. This is achieved

- elimination of the initial phase of a sharp increase in the polymerization rate and its subsequent decrease,

- constant polymerization rates for 6 to 8 hours, that is, the residence time in continuous reactors,

- prevention of deposits on the inner walls of the polymerization device,

- high polymer bed weight, ensuring high polymerization productivity,

- absence of dust content in the polymer and particles with a diameter below 0.1 mm,

- high bulk density of polymer powder (450 to 480 kg/m ¹ ),

- possibilities to regulate the properties of the polymer by the type of catalytic system used and the polymerization conditions,

- stability of catalyst activity over many months to years and its resistance to electron donor type impurities.

- improvement of the rheological properties of the polymer compared to polymers not containing paraffinic hydrocarbon.

The invention will be illustrated by the following examples of the preparation of catalysts. The % in the examples are by weight unless otherwise stated.

Example 1 and 2

Into a cleaned reactor containing 50 ml of stripped n-heptane, 2 g of silica containing 0.5 mmol of hydroxyl groups per 1 g were poured against the stream of pure nitrogen, and a measured amount of organoaluminum and organomagnesium compounds I was added - ratios see Table 1. After about 30 minutes of reaction at normal temperature, a determined amount of transition metal compound II (TiCl^ - example 1 and VCl^ - example 2) was measured and stirred for another 30 minutes. Then, an amount of paraffin with a melting point of 48 to 50 °C was added according to Table 1. After its dissolution with constant stirring, the solvent was removed by evacuation. The product was an almost white powder, with mechanical properties similar to the starting silica.

Example 3

In a 100 ml glass reaction vessel, 50 ml of n-heptane was purified by bubbling ultrapure nitrogen at a temperature of 80 to 90 °C to evaporate about 15% of the original amount of n-heptane. 2.0 g of Davison 952 silica, activated by passing ultrapure nitrogen for 4 hours at a temperature of 600 °C, were added. 1.2 mmol of triethylaluminum was added at room temperature in the form of a solution in a hydrocarbon. After about 30 minutes of stirring, 0.24 mmol of TiCl^ was added and the suspension was stirred again for 30 min. Finally, the organomagnesium compound - 0.24 mmol of butylethylmagnesium in the form of a solution in a hydrocarbon was added. After another 30 minutes of stirring, a mixture of ethylene with 60% by volume hydrogen was introduced into the suspension so that 50 mmol of ethylene polymerized into oligomers that were solid at room temperature. After the completion of this prepolymerization, the greater part of the solvent was removed by evacuation so that a free-flowing, easily mobile powder was formed. About 3.6 g of a supported single-phase catalyst capable of polymerizing 1-alkenes at a high rate without the need for additional activation just before polymerization or in the polymerization reactor was formed. The catalyst is non-sticky at room temperature, resistant to the diffusion of impurities and can be stored practically indefinitely before polymerization.

Example 4

In a 100 ml glass reactor, n-heptane was stripped so that after evaporation of at least 15% of the volume, 50 ml remained. 2 g of silica containing 0.75 mmol of hydroxyl groups per 1 g were poured into n-heptane against a nitrogen stream, and a measured amount of organoaluminum compound or their mixture I according to Table 1 was added. After about 30 minutes of stirring at laboratory temperature, titanium compound II was added. The suspension was stirred again for 30 minutes, after which the organomagnesium compound was dosed in the form of a heptane solution with paraffin with a melting point of 53 °C to 55 °C. After another 30 minutes of stirring, n-heptane was removed by purging with pure nitrogen until an almost white loose catalyst was obtained.

ExampleS

The procedure is the same as in Example 3 except that instead of triethylaluminum, a mixture of ethylaluminum dichloride and diethylaluminum chloride according to Table 1 was used, instead of TiCl^, Ti(OEt)^ was used, and instead of butylethylmagnesium, dibutylmagnesium was used in the proportions according to Table 1. After the end of the application of the organomagnesium component, 40 mmol of 1-butene with 10 mmol of hydrogen was added and stirring was continued at normal temperature until the complete polymerization of 1-butene. After the end of the prepolymerization, most of the heptane was removed by blowing nitrogen through, and 4.2 g of a supported single-phase catalyst active in the polymerization of 1-alkenes was formed without the need for additional activation by any other component.

I

Example 6

The procedure is the same as in Example 3, except that the components according to Table 1 were used for the preparation and after applying dibutylmagnesium and stirring for about 30 min, 20 mmol of 1-hexene with 5 mmol of hydrogen were added, the mixture was heated to 50 °C with stirring and stirring was continued for 2 h. With a strong stream of nitrogen directed to the bottom of the vessel while maintaining the temperature at 50 °C, the excess solvent was evaporated and 4.0 g of a supported single-phase catalyst capable of polymerizing ethylene without the need for additional activation with an organometallic compound were obtained.

Example7a8

The procedure is the same as in Example 1. Except that 2.0 g of alumina containing 0.75 mmol of hydroxyl groups per gram was used, and after the components according to Table 1 were applied, instead of ethylene, 10 mmol of 1-octene (Example 7) or 5 mmol of 1-decene (Example 8) together with 2 mmol of hydrogen were sprayed into the reaction vessel. The mixture was heated to 80 °C and stirring was continued for 4 hours. The excess solvent was then evaporated with ultrapure nitrogen. About 3.5 g of a supported single-phase catalyst capable of polymerizing 1-alkenes was obtained.

Example 9

60 ml of n-heptane, 2 g of paraffin with a melting point of 55 to 57 °C and 2.0 g of Davison 952 silica, activated with ultrapure nitrogen for 4 h at 800 °C, were added to a 100 ml glass reaction vessel, the suspension was heated to 80 to 90 °C and 10 ml of n-heptane was evaporated by bubbling ultrapure nitrogen. 1.43 mmol < · . l of aluminum dichloride in the form of a solution in n-heptane was added to the suspension and after 30 min of stirring 0.19 mmol of TiCl^. N.. stirring was continued for about 30 min, after which 0.76 mmol of butylethylmagnesium was added. After brief stirring, n-heptane was evaporated to the stage of a white free-flowing powder.

The catalysts of the floated poodles of examples 1 to 9 can be obtained in the form of dry and free-flowing powders containing a small amount of low molecular weight solvent up to a maximum of about 50%. The catalysts can be stored indefinitely in commonly used containers using conventional valves or taps. In the event of penetration of impurities of electron donor types to the catalysts, it is necessary to thoroughly purge the catalyst bed with ultrapure nitrogen before polymerization to prevent impurities from entering the polymerization equipment.

Polymerizations were carried out according to the following example:

Example 10

The powder catalyst is placed sealed in a glass ampoule in the crushing device of a laboratory reactor with a volume of 1.5 l, which allows the preparation of 300 g of polymer. The reactor was purged with a flow of ultrapure nitrogen overnight (16 hours), then it was alternately pressurized with nitrogen to 2 MPa at the temperature of the future polymerization 5 times and evacuated, after which it was pressurized twice with ethylene to 2' MPa and evacuated again. Finally, the reactor was pressurized with a mixture of monomers with hydrogen - see Table 2 for ratios. The polymerization began by crushing a glass flask containing 50 to 100 mg of catalyst. The fluid layer was kept in suspension by mechanical stirring, the polymerization rate was measured from the consumption of the supplied monomer mixture. After a certain time (usually 4 hours) the reactor was depressurized, opened and the polymer isolated.

After deactivating the catalyst with air, steam or carbon monoxide, the polymers must be stabilized against UV radiation and oxidation at higher temperatures with conventional stabilizers.

For example, a mixture of a sterically hindered phenolic antioxidant and tris-(nonylphenyl)phosphite in a weight ratio of 1:0.5 to 1.5 in an amount of 0.01 to 0.03% per polymer can be used. Due to the high activity of the catalysts, the amount of stabilizers required is low. The polymer is made up of large particles (mostly 0.5 mm and larger), so it does not need to be granulated by processing.

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Claims (2)

subject to finding CLAIMS 1. Catalyst for the polymerization of 1-alkenes, obtainable by sequential deposition on an inert inorganic silicon and / or aluminum oxide of at least one organic aluminum compound and optionally magnesium, at least one transition metal compound 4a and 5a of the periodic group and optionally at least one organic magnesium compound; characterized in that it contains 0.5 to 50% by weight of a paraffinic hydrocarbon having a melting point of 25 to 150 ° C. 2. Catalyst for the polymerization of 1-alkenes according to claim 1, characterized in that the paraffinic hydrocarbon is a product of prepolymerization of 1-alkene on an active catalyst.