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    • 专利摘要:
    1. Catalyst for the polymerization of olefins, including the magnesium-containing component and the transition metal trichloride - titanium trichloride or a mixture of titanium trichloride and vanadium trichloride in a molar ratio of 1: 1g, characterized in that, in order to increase the thermal stability of the catalyst, the magnesium-oxide. at least one compound selected from magnesium monohalide, magnesium hydrohalide, organomagnesium, magnesium hydride, and co-. its tav corresponds to the following empirical formula: (NMdH) (mdX2) and (mdH) (OK), where R I and n is C4H9; X - Ce, Vg, and 0.03 - L.45, b O - 0.19, with 0 - 0.23, with an atomic ratio of magnesium to transition metal 1-25. 2. Catalytic system for the polymerization of olefins containing magnesium-containing component, trichloride. transition metal - titanium trichloride or a mixture of titanium trichloride and trichloride. Vanadium in a 1: 1 molar ratio and an activator, characterized in that, in order to increase the thermal stability of the system, the system includes, as a magnesium-containing component, at the edge; At least one compound selected from magnesium monohalide, magnesium hydrohalide, organomagnesium compound, magnesium hydride, and its composition I corresponds to the following empirical formula: (HMdX) (MgXj) a (MgSj) (ORj) J s,. Rde R - n - n - X - ce, Br, S 0.03 - 0.45, b O - 0.19, with O - 0.23, As an activator, the co-D1 system holds a compound selected from a ch group, including trioctylaluminum, dimethylethyldiethylsiloxalane, 1C tetraisobutylaluminoxane, with an atom of magnesium to transition metal ratio of 1-25 and atomic ratio of activator metal to transitional metal of 0.3-100. 3. A method for preparing a catalyst for the polymerization of olefins, comprising co-grinding in an anhydrous medium of the magnes containing component and the transition metal trichloride — titanium trichloride or a mixture of: titanium trichloride and vanadium trichloride in a molar ratio of 1: 1, which is catalyst with improved heat resistance,
    公开号:SU1055320A3
    申请号:SU792760904
    申请日:1979-05-04
    公开日:1983-11-15
    发明作者:Бюжадукс Карел
    申请人:Сосьете Шимик Де Шарбоннаж (Фирма)；
    IPC主号:
    专利说明:

    The magnesium component is conveniently obtained by thermal decomposition of a powdered organomagnesium halide with a general formula:
    RMgX
    where R - n -. n - C4 Nd;
    X - se, wg,
    and grinding is carried out at the atomic ratio of magnesium "-K transition metal 1-25.
    4. Method of polymerization of ethylene or copolymerization of ethylene with propylene at elevated temperature in a suspension of an inert liquid hydrocarbon containing at least 6 carbon atoms, in the presence of a catalytic system comprising the magnesium component, transition metal chloride - titanium trichloride or a mixture of titanium trichloride and Vanadium trichloride in a molar ratio of 1: 1 and an activator, o tl and h and y and, in order to obtain polymers with improved mechanical properties, the polymerization of ethylene or copolymer ization of ethylene with propylene is carried out at a temperature of 80-260S, a pressure of 1-1300 bar, in the presence of a catalyst system comprising as components Magnesium, at least one compound selected from monohalide. magnesium, magnesium hydrohalide, organomagnesium, magnesium hydride, and the corresponding empirical formula:
    (NMdH) (MgX2) a (MgH.;) (OR) with
    where R - n - a - X - CS, Br; a 0.03 - 0.45, b 0 t 0.19,. c - o - o, 2 3,
    as an activator, a compound selected from the group including aluminum trioctyl, dimethylethyldiethylsiloxane, tetraisobutylaluminoxane with an atomic ratio of magnesium to transition metal of 1-25 and atomic ratio from carrying the metal of activator to the transition metal of 0.3-100, with the duration of the catalytic system in the process of polymerization 3.0-75 C.
    The invention relates to catalysts, congestions for the polymerization of olefins, to catalytic systems based on them, as well as to methods for producing catalysts for the polymerization of olefins and methods for the polymerization of ethyl or its copolymerization with propylene.
    A catalyst for the polymerization of olefins-α, which is a product of the interaction of magnesium chloride with titanium tetrachloride, and a catalytic system for the polymerization of olefins on the basis of the product and the organo-aluminum compound ij is known.
    A method is known for producing said catalyst by reacting magnesium chloride, used in the form of particles with a size of 50-200 µm and a content of water of crystallization of 0.5-3.5 mol per mole of magnesium chloride; with titanium tetrachloride at boiling temperature of titanium tetrachloride for 1 hour, followed by washing successively with titanium tetrachloride and heptane.
    The known method of polymerization of olefins in an environment of inert liquid hydrocarbon g} ri 75-85 C and pressure
    5.5-7.5 kg / cm2 in the presence of a catalytic system containing the product of the interaction of titanium tetrachloride with magnesium chloride and an organoaluminum compound — triisobutylaluminum ij.
    The disadvantage is. “The solution is the need to use magnesium chloride with strong characteristics (particle size and crystalline content of Zion water), which leads to complication of the catalyst preparation technology, poor mechanical properties of the polymers obtained (relatively low resistance of polymer particles to crushing and pressing)
    Closest to the proposed technical technical and achievable effect are a catalyst for the polymerization of olefins, containing the magnesium-containing or zinc-containing component of the transition metal tritrichloride or a mixture of titanium trichloride and vangsch trichloride in a molar ratio of 1: 1, catalytic: K a system for polymerizing olefins containing magnesium containing or a zinc-containing component, a transition metal trichloride — titanium trichloride or a mixture of titanium trichloride and vanadium trichloride in a molar ratio G: 1 and act Vator - with union of selected from the group including sistent with dialkylaluminum chloride, alkildihloridalyuminy, wherein alkyl - ethyl or butyl; A method for preparing a catalyst for the polymerization of olefins by co-grinding in an anhydrous medium magnesium. containing or zinc-containing components (magnesium or zinc halide) and transition metal trichloride — titanium trichloride or a mixture of titanium trichloride and vanadium trichloride in a molar ratio of 1; 1 to form an active powder; to the right of the diffraction line, the KoTopoi o spectrum has the highest intensity powders of ordinary halides is a less intense line that is replaced by a greater or lesser halo: also a method for the polymerization of olefins at 85–100 ° C in a suspension of an inert liquid hydrocarbon containing Shorter 6 carbon atoms at a pressure of 8-10 atm in the presence of a catalytic system comprising a magnesium or zinc-containing component / transition metal trichloride — titanium trichloride or a mixture of titanium trichloride and vanadium trichloride in a 1: 1 ratio and di a.ini ictJuuiYuinnnA. | Chloe |) Idealuminium d. However, the known solutions are characterized by insufficient thermal stability of the catalyst and the catalytic system based on it, and polymers are obtained with insufficiently high mechanical properties. Thus, the catalysts are stable up to 230-250 C and with teMnepaType above 250 s /, the stability of the catalyst decreases, which leads to a decrease in polymer yield by 50%. This polymerization method of olefins makes it possible to produce polymers having a tensile strength of 270-280 kg / Cm and bending strength of 170-195 kg / sec. The purpose of the invention is to increase the thermal resistance of the catalyst and the catalytic system based on it, as well as to obtain polymers with improved mechanical properties. This goal is achieved by the fact that the catalyst for the polymerization of olefins contains a magnesium-containing component, including at least one compound, selected from magnesium monohalogenide, magnesium hydrohalide, organomagnesium compound, magnesium hydride, and its composition corresponds to the following empirical formula: (NMDX) MgX9) a {MgH.2) btMg (ORj) with, where R is n - CaH,; H - C4No; X - CE, Br, and 0.03 - 0.45, b O - 0.19, with O - 0.23, and transition metal trichloride titanium trichloride or a mixture of titanium trichloride and vanadium trichloride in a molar ratio of 1: 1, with atomic ratio of magnesium to transition metal 1.-25. The catalytic system for the polymerization of olefins contains a magnesium-containing component, including at least one compound selected from magnesium monohalogenide, magnesium hydrohalide, organomagnesium compound, magnesium hydride, and its composition corresponds to the following empirical formula: (NMDX) (MDC ) (MDN) b Md (s, where R is n - 0 -,%;. N - S. But; X - se, Br / a 0.03 - 0., 45, b O g: 0.19, with 0 -, transition metal trichloride - titanium trichloride or a mixture of titanium trichloride and vanadium trichloride in a molar ratio of 1: 1 with an atomic ratio of magnesium in n Transition metal 1-25 and activator g compound selected from the group consisting of trioctylaluminum, dimethylethyldiethylsiloxalane, tetraisobutylaluminooxane, with an atomic ratio of activator metal to transition metal of 0.3-100. A method for preparing a catalyst for polymerizing olefins includes preliminarily preparing magnesium. decomposition at 210-330 ° C of the porous halide of an organomagnesium compound of the general formula: where R is n-SLN; n - SrNr; X - se, Br; and joint grinding in the anhydrous medium of the magnesium-containing component and the transition metal trichloride of titanium trichloride or a mixture of titanium trichloride and vanadium trichloride in a molar ratio of 1: 1, with an atomic ratio of magnesium to transition metal of 1-25. - A method for the polymerization of ethylene or the copolymerization of ethylene with propylene is carried out at 80-260 ° C, a pressure of 1/1300 bar in a suspension of an inert liquid hydrocarbon containing at least b carbon atoms, in the presence of a catalytic system containing magnesium, containing a component containing at least one compound, c. phosphate of magnesium monohalide, magnesium hydrohalide, organomagnesium compound, magnesium hydride, and corresponding to the following empirical formula: (HMdX) (MgXj) a (Mdn) (OR,)} s, where R is n - Cahn; n X - se, Br and 0.03 - 0.45; b 0.- 0.19 ;, with O - 0.23, the transition metal trichloride — three chloro-titanium or a mixture of titanium trichloride and vanadium trichloride with a molar ratio of 1: 1 and an activator — a mixture selected from the group including aluminum, dimethylethylsiloxalane, tetraisobutylalumine ocean, with an atomic ratio of magnesium and a transition metal of 1-25 and an atomic ratio; the activator to the transition metal is 0.3-100, with a duration of stay of the catalytic system in the polymerization process 30-75 s. The invention allows to significantly increase the thermal stability of the catalyst and the catalytic system based on it. Thus, the proposed catalysts have thermal stability down to. The proposed polymerization method allows to obtain polymers with improved mechanical properties, such as a tensile strength (330-355 kg / cm) and a flexural strength of 260 kg / cm. The proposed catalysts are the product obtained by contacting: a) a compound of magic comprising at least one type of dyno Y compound selected from the monohalogen of magnesia magnets MdH (where X is halogen), hydrohalides of magnesium ndshh and hydrides of magnesium Md%, moreover, this type of compound Y, when it is YMdX or MdH, is formed by thermal decomposition of the powdered organomagnesium halide; b) at least one transition metal halide, titanium and vanadium, and the valence of the metal of this halide is three, and the corresponding number of compounds (a) and (b) is such that the actual ratio of magnesium to the specified metal is em 1-25. Halides (b) used according to the invention; in particular, titanium trichloride Tic € g, predominantly crystallized together with aluminum chloride as a compound of the formula TiCE 1/3 AICI, called violet titanium trichloride: trichloride vaadi VCgj; and mixtures of these halides with each other. Compounds (a) are magnesium hydride, MdH, and the product is obtained by thermal decomposition of a powdered organomagnesium compound of the formula R, MdH, where R is - and - n -; . X - Sat. Terche decomposition of organomagnesium compounds under conditions of temperature control leads to ObraO; Vania, first of all, compounds of the ShdH type, having the formula: (HMdH) (MdHg) a (MgH2) (OR2) c. Pos: leDz SVdee thermal decomposition of organomagnesium compounds of halides under temperature control conditions leads to the formation of compounds of the MdH type, having the formula (MdH) (MdX2) a (Mg) b (MgO) c, / where a, b and c have the above values. The complex formulas of the type HMdH and MdH of the compounds proposed are explained by the complex nature of the powdered halogenates of the magnesium orium compounds from which they are formed. . The contacting of compounds (a) and (b) is the joint grinding of these compounds in a completely anhydrous medium for a sufficient period of time, the duration of which is determined directly by the specialist conducting the process. Compounds (a), incorporated into the catalyst, are characterized by an increased specific surface area. Compounds where Y is a magnesium hydrohalide of the formula HMdX have a specific surface area, determined using a calibrated sorption meter, more than 150, Compounds where Y is a magnesium monohalogenide MdH, have a specific surface area, determined by the same method, more than 50. If, in the preparation of catalysts (by contacting compounds (a) and (b)), compound (a) is MDM}, which is a commercial product, then it is only necessary to carefully monitor that it is completely anhydrous before contacting it with the compound (b). ). If compound (a) is a compound of the type HMdH. Or MdH, then first (at the first stage) a powdered halide of the organofluorine compound is obtained, at the second stage the thermal decomposition of the said powdered organomagnesium halide compound under conditions of temperature control and at the third stage - contacting the produced decomposition product with at least one halide (b). Temperature control is that the temperature in the second stage is selected as a function of the organomagnesium halide, which is obtained at the first stage, especially as a radical. halogenide, wil. Functions of the type of compound: Y, which is advisable to bring into contact with halogen house (b) in the third stage. So, when the radical R; f is. an aliphatic group, the decomposition of the poryoxyphalylgenide of the organomagnesium compound occurs in two steps as the temperature rises. When the temperature reaches 170-220 ° C, then decomposition produces a product of the type YMdX, having the above formulas. When the temperature rises more, the ratio continues and the compound of the type HMdH is converted to the compound MdH of the above formula. :; .., The proposed catalysts are used for the polymerization of olefins, especially ethylene, when they are part of a catalytic system / including, in addition, an activating agent selected from among hydrides and organometallic compounds of metals of groups 1-3 a system of elements in such an amount that the atomic ratio of the metal of the specified activating agent to the transition metal catalyst is 0.3-10.0. The most preferred activating agents are trialkyl; aluminum compounds and alkylsilanes. A method of polymerizing ethylene or copolymerizing it with propylene is carried out at 80-260 s, a pressure of 1-1300 bar in the presence of the described catalytic system. The temperature and / or polymerization pressure n is too high in the presence of an inert carbon of hydrogen having less than 5 carbon atoms such as propane or butane. Under high pressure, the average residence time of the catalytic system in the 30-oz polymerization reactor is 75 seconds, it depends on the temperature developed in the reactor, and the duration is greater, the lower the temperature. Very often, to regulate the flow index of a polymer, especially polyethylene, polymerization is carried out in the presence of a chain transfer agent such as hydrogen. At high pressure, this agent is used in an amount of 0.04-2% by volume of the amount of ethylene. A characteristic feature of the method of using hydrogen with hydrogen is that the flow index of the polymer is extremely sensitive to the amount of hydrogen introduced and varies significantly as a function of the amount of hydrogen. The proposed method of polymerization or copolymerization. ethylene allows a series of polymers to be obtained, the density of which is O, 905-0.960 g / cm, and the yield index of the polymer is 0.1-100 dg / min. The relatively low-density polymers, tfa example 0.905-0.935 g / cm, are obtained by copolymerizing ethylene. with. L-olefin, for example with propylene, in the amount of 15-33 wt.%. The proposed method provides the possibility of producing 11 polymer-1B ethylene with a flow index of about 0.1-2 dg / min, having a high content of: Limer compounds with high molecular weight, which improves their mechanical properties: (resistance, thinning, bending strength) . Measures 1. Vertical cylindrical reactor with a capacity of 750 Mrt, equipped with a lattice, and three holes each with a diameter of 1 ml / cm are filled with 520 g of magnesium in the lower part in the form of small cylindrical particles 3-4 mm long, cut out from magnesium wire. In the upper part of the reactor serves with a flow rate of 15 ml / h through the feed pump a-butyl chloride. A dry nitrogen flow directed to it into the lower reactor vessel. The magnesium particles are mixed by means of a mechanical stirrer. Maintaining the lattice temperature of 125 s, a completely white n-butyl magnesium chloride powder with a capacity of 13 g / h is obtained. .This, 6m powder is first degassed under reduced pressure and 50 ° C with the purpose of removing accidentally cooled gases, as well as all volatile substances. In practice, the outgassing process is not necessary, since "the weight loss of the sample during such processing is less than 1%.
    The powdered powder was then introduced into a furnace, at which the temperature was maintained at 219 ° C, where it was located for 3 hours. The decomposition gases, consisting of a mixture of butanes and butanes, were periodically analyzed by gas chromatography. A quantitative analysis of the constituent components of these gases, carried out in conjunction with the weight analysis and thermogravimetric analysis of the initial powder, allows us to establish the following formula for the thermally decomposed powder:
    . (NMdCyo) (Mgce, j). (MgH) The specific surface, measured: by means of a calibrated sorption meter according to standard methods, is 154. I Example2. In the apparatus described in Example 1, n-butyl bromide (35 ml / h) is passed through magnesium to form coarse particles while maintaining the temperature of the lattice at 120 s. A white nopoidoK n-butyl magnesium bromide and with a capacity of 50 g / h is obtained, which is subjected to degassing at 50 ° C, and this powder is heated for 4.5 hours in an oven at. The quantitative analysis of decomposition gases, carried out by gas chromatography, and the weight analysis and thermogravimetric analysis of the initial powder carried out together with it allow us to establish the following formula of the thermally decomposed powder:
    (NMdVg) (mdVg, 2)
    Froze Powdered n-butyl magnesium is obtained: h "loride with a productivity of 13.7 g / h according to example 1, starting from 16 ml / h of n-butyl chloride, while the temperature of the lattice is maintained at 130 ° C.
    The obtained powder is subjected to weight analysis, and then degassed with and introduced into the furnace. The furnace was maintained at 210 C 3.5, after which the weight loss of the powder was 40.33%, then the temperature was maintained at 3 hours, after which the weight loss was 40.76%. These data, together with the weight analysis data, allow to establish the following formula for the powder obtained as a result of decomposition at
    (MDS) (Mgce, j) o, 5 (MgHjJo tf i
    The surface area of this powder is measured by a calibrated sorption meter according to a standard method 54.
    PRI me R 4. Get powdered n-butyl magnesium chloride with a productivity of 7 g / h according to example 1, but starting from 12 ml / h of a solution of about 20 mol.% N-butanol in butyl chloride. The obtained powder is subjected to weight analysis, then degassed at 50 ° C and introduced into the furnace. The furnace temperature was maintained at 5 hours, after which the weight loss of the powder was 27.4%. These data, together with the weight analysis data, allow to establish the following formula for the thermally decomposed powder:
    (HMgCeKMgCe2 o.45 (WgH2lo.05 (W (OC4H, (24o, 23
    Examples 5-14. The compound (a) of the proposed catalyst, consisting either of powdered compounds corresponding to examples 1-4 or of magnesium hydride (MgHj) as an anhydrous powder, is subjected to grinding together with violet titanium chloride — AbCbd.
    TYTANYUM in the form of the trademark TAG 191. (The amount of violet titanium chloride, the atomic ratio Mg / Ti is shown in Table 1. The quantities are given in parts by weight). The catalyst thus prepared is converted into suspension in hydrocarbons fractions (2 and activated with trioctyl aluminum to obtain an atomic ratio AI / Ti equal to 8.
    600 ml of the indicated hydrocarbon fraction-C are introduced into a 1-liter autoclave reactor made of steel (2, ethylene is introduced to a saturation state at a pressure of 6 bar, then a previously prepared catalyst suspension. Polymerization of ethylene is carried out at 1 min constant pressure of ethylene is 6 bar. After that, the solution is regenerated and the polymer is recovered after cooling by filtration. The catalytic yield of product Rcf, expressed in grams of polymer per gram of titanium per minute per
    one atmosphere table.1.). I.
    Example 15-17. The compound (a) of the proposed catalyst, combined with the powdered compounds of the examples 2-4, was ground together with titanium chloride TAC 191 (see Table 1) to bring the Mg / Ti atomic ratio to 2. The prepared catalyst was suspended. in hydrocarbons, fractions C (Cf and activated with trionyl aluminum to bring the atomic ratio AI / Ti to 100), 600 ml of the indicated fraction C are introduced into a 1 liter reactor (after which ethylene is introduced to saturation at atmospheric pressure, and then preliminarily prepared catalyst suspension. Polymerization of ethylene is carried out at 80 ° C for 1 hour while maintaining a constant pressure of 1 bar. After this period, the solution is regenerated, and after cooling, the polymer is removed by filtration. The catalytic yield of the product is determined (Table 1). Examples 18-5b Compound, (a) of the catalyst according to the invention, either from powdered compounds according to examples 1. and 3, either from magnesium hydride MDH2 as an anhydrous powder, is subjected to grinding for 2 hours together with titanium chloride violet TAC 191 (in example 18, it is replaced with a random mixture of TAS 191 with vanadium trichloride) to bring the atomic ratio Mg / Ti / Mg / Ti + V in example 18 to the value specified in table.1. The prepared catalysts are converted into a slurry in a hydrocarbon fraction of -.C. fn-C 2 and activate dimethylsteldistil / force / oxalandm until obtaining an atomic ratio AB / Ti / Aff iTi + V in example 18 equal to 8 (for. (Except for examples 21 and 22, in which AB / T1 is 4 "OZ), respectively. Ethylene is then polymerized under the same conditions as in Examples 5-14, and the catalytic yield of product RC is determined. Examples 27-40. The catalyst obtained by joint grinding of magnesium and titanium components under the conditions of examples 5-14 and dispersed in meth licyclohexane and activate either trioctyl - aluminum activating agent A), Lee bo-dimethylethyldistilsiloxalane; (activating agent I) to obtain the atomic ratio Av / Ti equal to b (except for example 34. in which the atomic ratio A8 / T1 is 4 Next a continuous polymerization process of ethylene under a pressure of 400 bar (600 bar in examples 33-35) in a 0.6 l autoclave reactor maintained at temperature T, and introducing a previously prepared catalyst dispersion into it at such a flow rate of this catalyst that if its average residence time in the reactor was about 30 seconds. Hydrogen is introduced into the reactor to control the index of the currently formed polymer. : Table 2 shows the process conditions (the catalytic yield of the product RC is expressed in kilograms of polyethylene per milliatric titanium, for example 33 per milliatom of titanium and vangshchi, the flow index of the polymer, the molecular distribution index is defined as the ratio of the weight average molecular weight to the average number molecular weight Mw / Mn, this ratio being determined by gel permeation chromatography). Examples 41 - and 42. Ethylene is subjected to polymerization in a cylindrical autoclave reactor, in which the temperature is maintained. and pressure 1300 bar. The catalysts used in this case are the same as. in example 5 (for example 41) and the product obtained by the joint grinding of TAC 191 and anhydrous magnesium dichloride, having an Mg / Ti atomic ratio of 10 (for comparative example 42). These catalysts are activated with trioctyl aluminum to give an AP / Ti ratio of 3. The average residence time of each catalyst system in the reactor is 40 seconds. Table 3 shows the data for examples 41- .46 (the content of polymer compounds with very high MO, medical weights is expressed in thousand hours and is determined by gel permeation chromatography, the tear resistance RR is expressed in kg / cm and the bending strength, RLF - in kg / cm). Examples 43-46. Ethylene under; ver1: polymerization under pressure of 1000 bar in an autoclave reactor with a stirrer divided into three zones of the same volume. The first zone, to which the catalyst is fed and 1/3 of the total monomer, is maintained at 210 ° C; the second zone, to which only 1/3 of the monomer is supplied from the total amount, is maintained at 180 ° C and the third zone, into which the catalyst and 1/3 of the monomer is supplied from the total amount, is maintained at 260 C. The catalyzers used are the same, as in examples 25 (for example 43), 8 (dl. example 44) and 12 (for example 45), and the product obtained by joint grinding of TAC 191 and anhydrous magnesium dichloride has an Mg / Ti atomic ratio of 3 ( for comparative example 46). These catalysts are activated when the atomic ratio is herbal 3 with the appropriate activating agents (activating agent A in examples 44-46, activating agent B in example 43). The average residence time of each catalytic system in the reactor is 75 cv. EXAMPLE 47. Using the apparatus according to examples 27-40, prevent the blending of ethylene with propylene.
    Conditions of polymerization include the following mixture composition wt.%: Ethylene propylene 29.5, hydrogen 0.25 vol.%, Pressure. 600 bar, temperature l S С, catalyst and aktivator are used
    according to example 35. A copolymer is obtained with a catalytic yield: Rgs 2.4. Characterization of the copolymer: IF “7.7, M ,, 9рООр, М„ 18700, „, 4.8, density 0.937 r / cw ratio of methyl 21 CHj.
    table 2
    权利要求:
    Claims (4)
    [1]
    1. A catalyst for the polymerization of olefins, comprising a magnesium-containing component and transition metal trichloride — titanium trichloride or a mixture of titanium trichloride and vanadium trichloride in a molar ratio of 1: 1, characterized in that, in order to increase the thermal stability of the catalyst, the magnesium-containing component includes at least mercury, one compound selected from magnesium monohalogen., magnesium hydrohalide, organomagnesium compound, magnesium hydride, and its composition corresponds to the following empirical formula:
    (HMgX) (MdX 2 ) a (MgH 2 ) s [Mg (OR 2 )] c ,
    where r * and - C 3 H 7 ; nC4H9 7 X - se Wh but = 0,03 -L. 45 b = about - 0.19, from = about - 0.23,
    with an atomic ratio of magnesium to transition metal of 1-25.
    ’
    [2]
    2. A catalytic system for the polymerization of olefins containing a magnesium-containing component, trichloride. transition metal - titanium trichloride or a mixture of titanium trichloride and trichloride, vanadium in a molar ratio of 1: 1 and an activator, characterized in that, in order to increase the thermal stability of the system, as a magnesium-containing component, the system includes, at the edge; at least one compound selected from magnesium monohalide, magnesium hydrohalide, organomagnesium compounds, magnesium hydride, and its composition § it corresponds to the following empirical formula: · (HMgX) (MDX 2 ) a (MD8 ) 2 )] s,.
    ffle R - n - C 3 H 7 ; n - C 4.H9; x - ce, vg, a = 0.03 - 0.45, b = 0 g 0.19, c = 0 - 0.23, as an activator, the system contains a compound selected from the group consisting of trioctylaluminum, dimethylethyldiethylsiloxalane, tetraisobutylaluminoxane, when the atomic ratio of magnesium to the transition metal is 1-25 and the atomic ratio of the activator metal to the transition metal is 0.3-100.
    [3]
    3. A method of producing a catalyst for the polymerization of olefins, including co-grinding in an anhydrous medium a magnesium-containing component and a transition metal trichloride — titanium trichloride or a mixture: titanium trichloride and nadium trichloride I in a molar ratio of 1: 1, characterized in that, in order to obtain a catalyst with the above heat resistance, it is preliminarily obtained from 1055520 that the magnesium-containing component is obtained by thermal decomposition at 210-330 ° C of a powdered halide of an organomagnesium compound of the general formula:
    RMgX where R is n n is C4H9;
    X - ce, Br, and grinding are carried out with an atomic ratio of magnesium "-to transition metal 1-25.
    [4]
    4. A method of polymerizing ethylene or copolymerizing ethylene with propylene at an elevated temperature in a suspension of an inert liquid hydrocarbon containing at least 6 carbon atoms in the presence of a catalytic system comprising a magnesium-containing component, m ^ transition metal ichloride - titanium trichloride or a mixture of titanium trichloride and vanadium trichloride in a molar ratio of 1: 1 and an activator, about τη and especially with the fact that, in order to obtain polymers with improved mechanical properties, the polymerization of ethylene or copolymerization ethylene with propylene is carried out at a temperature of 80-2 ° C, a pressure of 1-1300 bar, in the presence of a catalytic system containing, as a magnesium-containing component, at least one compound selected from monohalide ', magnesium, magnesium hydrohalide, and organomagnesium compounds , magnesium hydride, and the corresponding following empirical formula:
    (HMgX) (MgXj) a (MdH ^) b [Mg (OR ^)] c where R - n - C ^ H 7 ; n - C4H4;
    X is CB, Br;
    a = 0.03 - 0.45, b = 0 t 0.19,. c = 0 - 0.23, as an activator - a compound selected from the group consisting of trioctylaluminium, dimethylethyldiethylsiloxalane, tetraisobutylaluminoxane with an atomic ratio of magnesium to transition metal of 1-25 and atomic ratio of activator metal to transition metal of 0.3-100 , with a residence time of the catalyst system in the polymerization process of 3.0-75 s.
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    同族专利:
    公开号 | 公开日
    JPS54146285A|1979-11-15|
    ES480215A0|1980-12-01|
    FR2424760B1|1982-02-26|
    DE2966524D1|1984-02-16|
    EP0005394B1|1984-01-11|
    ES8100615A1|1980-12-01|
    CS216239B2|1982-10-29|
    JPS5846203B2|1983-10-14|
    BR7902724A|1979-11-20|
    US4476288A|1984-10-09|
    EP0005394A2|1979-11-14|
    CA1122194A|1982-04-20|
    PT69452A|1979-05-01|
    US4263170A|1981-04-21|
    FR2424760A1|1979-11-30|
    EP0005394A3|1979-11-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3058969A|1962-10-16|Three-component metal hydride-transi- |
    CA906981A|1972-08-08|Montecatini Edison S.P.A.|Catalysts for the polymerization of olefins|
    IT603769A|1958-02-14|
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    GB1150640A|1966-12-23|1969-04-30|British Petroleum Co|Polymerisation Process|
    NL162661B|1968-11-21|1980-01-15|Montedison Spa|PROCESS FOR PREPARING A CATALYST FOR THE POLYMERIZATION OF OLEFINS-1.|
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    US4113654A|1971-04-20|1978-09-12|Montecatini Edison S.P.A.|Catalysts for the polymerization of olefins|
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    FR2241569B1|1973-08-21|1979-03-02|Ethylene Plastique Sa|
    FR2342306B1|1976-02-25|1980-05-30|Charbonnages Ste Chimique|
    JPS5745244B2|1976-09-02|1982-09-27|
    FR2370054B1|1976-11-09|1980-11-07|Charbonnages Ste Chimique|FR2370054B1|1976-11-09|1980-11-07|Charbonnages Ste Chimique|
    US4490514A|1983-08-16|1984-12-25|Chemplex Company|High-temperature ethylene polymerization and copolymerization using dialuminoxane cocatalysts|
    DE3504808A1|1985-02-13|1986-08-14|Studiengesellschaft Kohle mbH, 4330 Mülheim|METHOD FOR PRODUCING POLYOLEFINS, POLYDIENES AND THEIR COPOLYMERISATS|
    JP2006051489A|2004-07-12|2006-02-23|Sumitomo Chemical Co Ltd|Trimerization catalyst of olefin and trimerization method of olefin using this catalyst|
    KR100811116B1|2006-11-14|2008-03-06|한국과학기술연구원|Fabrication method of magnesium based hydrogen storage metarial|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7813416A|FR2424760B1|1978-05-05|1978-05-05|
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